Biomedical devices containing internal wetting agents

ABSTRACT

This invention includes a wettable biomedical device containing a high molecular weight hydrophilic polymer and a hydroxyl-functionalized silicone-containing monomer.

RELATED PATENT APPLICATIONS

This patent application claims priority of a provisional application,U.S. Ser. No. 60/318,536 which was filed on Sep. 10, 2001.

FIELD OF THE INVENTION

This invention relates to silicone hydrogels that contain internalwetting agents, as well as methods for their production and use.

BACKGROUND OF THE INVENTION

Contact lenses have been used commercially to improve vision since atleast the 1950s. The first contact lenses were made of hard materialsand as such were somewhat uncomfortable to users. Modern lenses havebeen developed that are made of softer materials, typically hydrogelsand particularly silicone hydrogels. Silicone hydrogels arewater-swollen polymer networks that have high oxygen permeability andsurfaces that are more hydrophobic than hydrophilic. These lensesprovide a good level of comfort to many lens wearers, but there are someusers who experience discomfort and excessive ocular deposits leading toreduced visual acuity when using these lenses. This discomfort anddeposits has been attributed to the hydrophobic character of thesurfaces of lenses and the interaction of those surfaces with theprotein, lipids and mucin and the hydrophilic surface of the eye.

Others have tried to alleviate this problem by coating the surface ofsilicone hydrogel contact lenses with hydrophilic coatings. For example,it has been disclosed that silicone hydrogel lenses can be made morecompatible with ocular surfaces by applying plasma coatings to the lenssurface. However, uncoated silicone hydrogel lenses having lowincidences of surface deposits have not been disclosed.

Incorporating internal hydrophilic agents (or wetting agents) into amacromer containing reaction mixture has been disclosed. However, notall silicone containing macromers display compatibility with hydrophilicpolymers. Modifying the surface of a polymeric article by addingpolymerizable surfactants to a monomer mix used to form the article hasalso been disclosed. However, lasting in vivo improvements inwettability and reductions in surface deposits are not likely.

Polyvinylpyrrolidone (PVP) or poly-2-ethyl-2-oxazoline have been addedto a hydrogel composition to form an interpenetrating network whichshows a low degree of surface friction, a low dehydration rate and ahigh degree of biodeposit resistance. However, the hydrogel formulationsdisclosed are conventional hydrogels and there is no disclosure on howto incorporate hydrophobic components, such as siloxane monomers,without losing monomer compatibility.

While it may be possible to incorporate high molecular weight polymersas internal wetting agents into silicone hydrogel lenses, such polymersare difficult to solubilize in reaction mixtures which containsilicones. In order to solubilize these wetting agents, siliconemacromers or other prepolymers must be used. These silicone macromers orprepolymers must be prepared in a separate step and then subsequentlymixed with the remaining ingredients of the silicone hydrogelformulation. This additional step (or steps) increases the cost and thetime it takes to produce these lenses.

Therefore it would be advantageous to find a lens formulation that doesnot require the use of surface treatment to provide on eye wettabilityand resistance to surface depositions.

SUMMARY OF THE INVENTION

The present invention relates to a wettable silicone hydrogel comprisingthe reaction product of at least one siloxane containing macromer; atleast one high molecular weight hydrophilic polymer; and at least onecompatibilizing component.

The present invention further relates to a ethod comprising the steps of(a) mixing reactive components comprising at least one high molecularweight hydrophilic polymer, at least one siloxane containing macromerand an effective amount of at least one compatibilizing component and(b) curing the product of step (a) to form a biomedical device.

The present invention further comprises a method comprising the steps of(a) mixing reactive components comprising a high molecular weighthydrophilic polymer and an effective amount of a compatibilizingcomponent and (b) curing the product of step (a) at or above a minimumgel time, to form a wettable biomedical device.

The present invention yet further relates to an ophthalmic lenscomprising a silicone hydrogel which has, without surface treatment, atear film break up time of at least about 7 seconds

The present invention still further relates to a silicone hydrogelcontact lens comprising at least one oxygen permeable component, atleast one compatibilizing component and an amount of high molecularweight hydrophilic polymer sufficient to provide said device, without asurface treatment, with tear film break up time after about one day ofwear of at least about 7 seconds.

A device comprising a silicone hydrogel contact lens which issubstantially free from surface deposition without surface modification.

DETAILED DESCRIPTION OF THE INVENTION

A biomedical device formed from a reaction mixture comprising,consisting essentially of, or consisting of a silicone containingmacromer, at least one high molecular weight hydrophilic polymer and acompatibilizing amount of a compatibilizing component.

It has been surprisingly found that biomedical devices, and particularlyophthalmic devices having exceptional in vivo or clinical wettability,without surface modification may be made by including an effectiveamount of a high molecular weight hydrophilic polymer and acompatibilizing amount of a compatibilizing component in a siliconehydrogel formulation. By exceptional wettability we mean a decrease inadvancing dynamic contact angle of at least about 10% and preferably atleast about 20% in some embodiments at least about 50% as compared to asimilar formulation without any hydrophilic polymer. Prior to thepresent invention ophthalmic devices formed from silicone hydrogelseither had to be surface modified to provide clinical wettability or beformed from at least one silicone containing macromer having hydroxylfunctionality.

As used herein, a “biomedical device” is any article that is designed tobe used while either in or on mammalian tissues or fluid and preferablyon or in human tissues or fluid. Examples of these devices include butare not limited to catheters, implants, stents, and ophthalmic devicessuch as intraocular lenses and contact lenses. The preferred biomedicaldevices are ophthalmic devices, particularly contact lenses, mostparticularly contact lenses made from silicone hydrogels.

As used herein, the terms “lens” and “opthalmic device” refer to devicesthat reside in or on the eye. These devices can provide opticalcorrection, wound care, drug delivery, diagnostic functionality orcosmetic enhancement or effect or a combination of these properties. Theterm lens includes but is not limited to soft contact lenses, hardcontact lenses, intraocular lenses, overlay lenses, ocular inserts, andoptical inserts.

As used herein the term “monomer” is a compound containing at least onepolymerizable group and an average molecular weight of about less than2000 Daltons, as measure via gel permeation chromatography refractiveindex detection. Thus, monomers, include dimers and in some casesoligomers, including oligomers made from more than one monomeric unit.

As used herein, the phrase “without a surface treatment” means that theexterior surfaces of the devices of the present invention are notseparately treated to improve the wettability of the device. Treatmentswhich may be foregone because of the present invention include, plasmatreatments, grafting, coating and the like. However, coatings whichprovide properties other than improved wettability, such as, but notlimited to antimicrobial coatings may be applied to devices of thepresent invention.

Various molecular weight ranges are disclosed herein. For compoundshaving discrete molecular structures, the molecular weights reportedherein are calculated based upon the molecular formula and reported ingm/mol. For polymers molecular weights (number average) are measured viagel permeation chromatography refractive index detection and reported inDaltons or are measured via kinematic viscosity measurements, asdescribed in Encyclopedia of Polymer Science and Engineering, N-VinylAmide Polymers, Second edition, Vol 17, pgs. 198-257, John Wiley & SonsInc. and reported in K-values.

High Molecular Weight Hydrophilic Polymer

As used herein, “high molecular weight hydrophilic polymer” refers tosubstances having a weight average molecular weight of no less thanabout 100,000 Daltons, wherein said substances upon incorporation tosilicone hydrogel formulations, improve the wettability of the curedsilicone hydrogels. The preferred weight average molecular weight ofthese high molecular weight hydrophilic polymers is greater than about150,000 Daltons; more preferably between about 150,000 to about2,000,000 Daltons, more preferably still between about 300,000 to about1,800,000 Daltons, most preferably about 500,000 to about 1,500,000Daltons (all weight average molecular weight).

Alternatively, the molecular weight of hydrophilic polymers of theinvention can be also expressed by the K-value, based on kinematicviscosity measurements, as described in Encyclopedia of Polymer Scienceand Engineering, N-Vinyl Amide Polymers, Second edition, Vol 17, pgs.198-257, John Wiley & Sons Inc. When expressed in this manner,hydrophilic monomers having K-values of greater than about 46 andpreferably between about 46 and about 150. The high molecular weighthydrophilic polymers are present in the formulations of these devices inan amount sufficient to provide contact lenses, which without surfacemodification remain substantially free from surface depositions duringuse. Typical use periods include at least about 8 hours, and preferablyworn several days in a row, and more preferably for 24 hours or morewithout removal. Substantially free from surface deposition means that,when viewed with a slit lamp, at least about 80% and preferably at leastabout 90%, and more preferably about 100% of the lenses worn in thepatient population display depositions rated as none or slight, over thewear period.

Suitable amounts of high molecular weight hydrophilic polymer includefrom about 1 to about 15 weight percent, more preferably about 3 toabout 15 percent, most preferably about 5 to about 12 percent, all basedupon the total weight of all reactive components.

Examples of high molecular weight hydrophilic polymers include but arenot limited to polyamides, polylactones, polyimides, polylactams andfunctionalized polyamides, polylactones, polyimides, polylactams, suchas DMA functionalized by copolymerizing DMA with a lesser molar amountof a hydroxyl-functional monomer such as HEMA, and then reacting thehydroxyl groups of the resulting copolymer with materials containingradical polymerizable groups, such as isocyanatoethylmethacrylate ormethacryloyl chloride. Hydrophilic prepolymers made from DMA or N-vinylpyrrolidone with glycidyl methacrylate may also be used. The glycidylmethacrylate ring can be opened to give a diol which may be used inconjunction with other hydrophilic prepolymer in a mixed system toincrease the compatibility of the high molecular weight hydrophilicpolymer, hydroxyl-functionalized silicone containing monomer and anyother groups which impart compatibility. The preferred high molecularweight hydrophilic polymers are those that contain a cyclic moiety intheir backbone, more preferably, a cyclic amide or cyclic imide. Highmolecular weight hydrophilic polymers include but are not limited topoly-N-vinyl pyrrolidone, poly-N-vinyl-2- piperidone,poly-N-vinyl-2-caprolactam, poly-N-vinyl-3-methyl-2- caprolactam,poly-N-vinyl-3-methyl-2-piperidone, poly-N-vinyl-4-methyl-2- piperidone,poly-N-vinyl-4-methyl-2-caprolactam, poly-N-vinyl-3-ethyl-2-pyrrolidone, and poly-N-vinyl-4,5-dimethyl-2-pyrrolidone,polyvinylimidazole, poly-N-N-dimethylacrylamide, polyvinyl alcohol,polyacrylic acid, polyethylene oxide, poly 2 ethyl oxazoline, heparinpolysaccharides, polysaccharides, mixtures and copolymers (includingblock or random, branched, multichain, comb-shaped or star shaped)thereof where poly-N-vinylpyrrolidone (PVP) is particularly preferred.Copolymers might also be used such as graft copolymers of PVP.

The high molecular weight hydrophilic polymers provide improvedwettability, and particularly improved in vivo wettability to themedical devices of the present invention. Without being bound by anytheory, it is believed that the high molecular weight hydrophilicpolymers are hydrogen bond receivers which in aqueous environments,hydrogen bond to water, thus becoming effectively more hydrophilic. Theabsence of water facilitates the incorporation of the hydrophilicpolymer in the reaction mixture. Aside from the specifically named highmolecular weight hydrophilic polymers, it is expected that any highmolecular weight polymer will be useful in this invention provided thatwhen said polymer is added to a silicone hydrogel formulation, thehydrophilic polymer (a) does not substantially phase separate from thereaction mixture and (b) imparts wettability to the resulting curedpolymer. In some embodiments it is preferred that the high molecularweight hydrophilic polymer be soluble in the diluent at processingtemperatures.

Manufacturing processes which use water or water soluble diluents may bepreferred due to their simplicity and reduced cost. In these embodimentshigh molecular weight hydrophilic polymers which are water soluble atprocessing temperatures are preferred.

Compatibilizinq Component

As used herein a “compatibilizing component” is a compound having anumber average molecular weight of about less than 5000 Daltons, andpreferably less than about 3000 Daltons, and containing at least onepolymerizable group, which is capable of solubilizing the selectedreactive components. Without a compatibilizing component the highmolecular weight hydrophilic polymer and oxygen permeable components areinsufficiently miscible, and cannot, with reasonable processingconditions, form an optically transparent ophthalmic device. Thecompatibilizing component of the present invention solubilizes theoxygen permeable component(s) and high molecular weight hydrophilicpolymer via hydrogen bonding, dispersive forces, combinations thereofand the like. Thus any functionality which reacts in any of these wayswith the hydrophilic polymer may be used as a compatibilizing component.Macromers (number average molecular weights of between about 5000 andabout 15,000 Daltons) may also be used so long as they have thecompatibilizing functionality described herein. If a compatibilizingmacromer is used it may still be necessary to add an additionalcompatibilizing component to get the desired level of wettability in theresulting ophthalmic device.

One suitable class of compatibilizing components of the presentinvention comprise at least one active hydrogen and at least onesiloxane group. An active hydrogen has the ability to hydrogen bond withthe hydrophilic polymer and any hydrophilic monomers present. Hydroxylgroups readily participate in hydrogen bonding and are therefore apreferred source of active hydrogens. Thus, in one embodiment, thecompatibilizing components of the present invention beneficiallycomprise at least one hydroxyl group and at least one “—Si—O—Si—”group.It is preferred that silicone and its attached oxygen account for morethan about 10 weight percent of said compatibilizing component, morepreferably more than about 20 weight percent.

The ratio of Si to OH in the compatibilizing component is also importantto providing a compatibilzing component which will provide the desireddegree of compatibilization. If the ratio of hydrophobic portion to OHis too high, the compatibilizing component may be poor atcompatibilizing the hydrophilic polymer, resulting in incompatiblereaction mixtures. Accordingly, in some embodiments, the Si to OH ratiois less than about 15:1, and preferably between about 1:1 to about 10:1.In some embodiments primary alcohols have provided improvedcompatibility compared to secondary alcohols. Those of skill in the artwill appreciate that the amount and selection of compatibilizingcomponent will depend on how much hydrophilic polymer is needed toachieve the desired wettability and the degree to which the siliconecontaining monomer is incompatible with the hydrophilic polymer.Examples of compatibilizing components include monomers of Formulae Iand II

wherein:

-   -   n is an integer between 3 and 35, and preferably between 4 and        25;    -   R¹ is hydrogen, C₁₋₆alkyl,;    -   R²,R³, and R⁴, are independently, C₁₋₆alkyl, triC₁₋₆alkylsiloxy,        phenyl, naphthyl, substituted C_(i-6)alkyl, substituted phenyl,        or substituted naphthyl where the alkyl substitutents are        selected from one or more members of the group consisting of        C₁₋₆alkoxycarbonyl, C₁₋₆alkyl, C₁₋₆alkoxy, amide, halogen,        hydroxyl, carboxyl, C₁₋₆alkylcarbonyl and formyl, and where the        aromatic substitutents are selected from one or more members of        the group consisting of C₁₋₆alkoxycarbonyl, C₁₋₆alkyl,        C₁₋₆alkoxy, amide, halogen, hydroxyl, carboxyl,        C₁₋₆alkylcarbonyl and formyl;    -   R⁵ is hydroxyl, an alkyl group containing one or more hydroxyl        groups, or (CH₂(CR⁹R¹⁰)_(y)O)_(x))—R¹¹ wherein y is 1 to 5,        preferably 1 to 3, x is an is an integer of 1 to 100, preferably        2 to 90 and more preferably 10 to 25; R⁹-R¹¹ are independently        selected from H, alkyl having up to 10 carbon atoms and alkyls        having up to 10 carbon atoms substituted with at least one polar        functional group;    -   R⁶ is a divalent group comprising up to 20 carbon atoms;    -   R⁷ is a monovalent group that can undergo free radical and/or        cationic polymerization comprising up to 20 carbon atoms; and    -   R⁸ is a divalent or trivalent group comprising up to 20 carbon        atoms.

Reaction mixtures of the present invention may include more than onecompatibilizing component.

For monofunctional compatibilizing components the preferred R¹ ishydrogen, and the preferred R²,R³, and R⁴, are C₁₋₆alkyl andtriC₁₋₆alkylsiloxy, most preferred methyl and trimethylsiloxy. Formultifunctional (difunctional or higher) R¹-R⁴ independently compriseethylenically unsaturated polymerizable groups and more preferablycomprise an acrylate, a styryl, a C₁₋₆alkylacrylate, acrylamide,C₁₋₆alkylacrylamide, N-vinyllactam, N-vinylamide, C₂₋₁₂alkenyl,C₂₋₁₂alkenylphenyl, C₂₋₁₂alkenylnaphthyl, or C₂₋₆alkenylphenylC₁₋₆alkyl.

The preferred R⁵ is hydroxyl, —CH₂OH or CH₂CHOHCH₂OH, with hydroxylbeing most preferred.

The preferred R⁶ is a divalent C₁₋₆alkyl, C₁₋₆alkyloxy,C₁₋₆alkyloxyC₁₋₆alkyl, phenylene, naphthalene, C₁₋₁₂cycloalkyl,C₁₋₆alkoxycarbonyl, amide, carboxy, C₁₋₆alkylcarbonyl, carbonyl,C₁₋₆alkoxy, substituted C₁₋₆alkyl, substituted C₁₋₆alkyloxy, substitutedC₁₋₆alkyloxyC₁₋₆alkyl, substituted phenylene, substituted naphthalene,substituted C₁₋₁₂cycloalkyl, where the substituents are selected fromone or more members of the group consisting of C₁₋₆alkoxycarbonyl,C₁₋₆alkyl, C₁₋₆alkoxy, amide, halogen, hydroxyl, carboxyl,C₁₋₆alkylcarbonyl and formyl. The particularly preferred R⁶ is adivalent methyl(methylene).

The preferred R⁷ comprises a free radical reactive group, such as anacrylate, a styryl, vinyl, vinyl ether, itaconate group, aC₁₋₆alkylacrylate, acrylamide, C₁₋₆alkylacrylamide, N-vinyllactam,N-vinylamide, C₂₋₁₂alkenyl, C₂₋₁₂alkenylphenyl, C₂₋₁₂alkenylnaphthyl, orC₂₋₆alkenylphenylC₁₋₆alkyl or a cationic reactive group such as vinylether or epoxide groups. The particulary preferred R⁷ is methacrylate.

The preferred R⁸ is is a divalent C₁₋₆alkyl, C₁₋₆alkyloxy,C₁₋₆alkyloxyC₁₋₆alkyl, phenylene, naphthalene, C₁₋₆cycloalkyl,C₁₋₆alkoxycarbonyl, amide, carboxy, C₁₋₆alkylcarbonyl, carbonyl,C₁₋₆alkoxy, substituted C₁₋₆alkyl, substituted C₁₋₆alkyloxy, substitutedC₁₋₆alkyloxyC₁₋₆alkyl, substituted phenylene, substituted naphthalene,substituted C_(1-u)cycloalkyl, where the substituents are selected fromone or more members of the group consisting of C₁₋₆alkoxycarbonyl,C₁₋₆alkyl, C₁₋₆alkoxy, amide, halogen, hydroxyl, carboxyl,C₁₋₆alkylcarbonyl and formyl. The particularly preferred R⁸ isC₁₋₆alkyloxyC₁₋₆alkyl.

Examples of compatibilizing component of Formula I that are particularlypreferred are 2-propenoic acid,2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[trimethylsilyl)oxy]disiloxanyl]propoxy]propylester (which can also be named(3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane.

The above compound,(3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilaneis formed from an epoxide, which produces an 80:20 mixture of thecompound shown above and(2-methacryloxy-3-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane.In the present invention the 80:20 mixture is preferred over pure(3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane.In some embodiments of the present invention it is preferred to havesome amount of the primary hydroxyl present, preferably greater thanabout 10 wt % and more preferably at least about 20 wt %

Other suitable hydroxyl-functionalized silicone containing monomersinclude(3-methacryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane

bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane

3-methacryloxy-2-(2-hydroxyethoxy)propyloxy)propylbis(trimethylsiloxy)methylsilane

N-2-methacryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silylcarbamate

N,N,N′,N′-tetrakis(3-methacryloxy-2-hydroxypropyl)-a,w-bis-3-aminopropyl-polydimethylsiloxane

The reaction products of glycidyl methacrylate with amino-functionalpolydimethylsiloxanes may also be used as a compatibilizing components.

Other suitable compatibilizing components include those disclosed incolumns 6,7 and 8 of U.S. Pat. No. 5,994,488, and monomers disclosed inU.S. Pat. Nos. 4,259,467; 4,260,725; 4,261,875; 4,649,184; 4,139,513,4,139,692; US 2002/0016383; U.S. Pat. Nos. 4,139,513 and 4,139,692.These and any other patents or applications cited herein areincorporated by reference.

Still additional structures which may be suitable compatibilizingcomponents include those similar to the compounds disclosed in Pro. ACSDiv. Polym. Mat. Sci. Eng., April 13-17, 1997, p. 42, and having thefollowing structure:

where n=1-50 and R independently comprise H or a polymerizableunsaturated group), with at least one R comprising a polymerizablegroup, and at least one R, and preferably 3-8 R, comprising H.

A second suitable class of compatibilizing components include thosehaving the structure given in Formula III, below:

IWA-HB-[IWA-HB]_(x)-IWA

Wherein x is 1 to 10;

IWA is a difunctional hydrophilic polymer as defined below, but having anumber average molecular weight of between about 1000 and about 50,000Daltons; and

HB is a difunctional moeity comprising at least one N which is capableof hydrogen bonding with active hydrogens in the hydrophilic polymer andany other component having active hydrogens.

Preferred IWA groups may be derived from {acute over (α)},ω-hydroxylterminated PVP and {acute over (α)},ω-hydroxyl terminatedpolyoxyalkylene glycols having number average molecular weights betweenabout 1,000 and about 50,000 Daltons.

Preferred HB groups include difunctional amides, imides, carbamates andureas, combinations thereof and the like.

Compatibilizing components of Formula III may be made by amineterminated polyoxyalkyleneglycols (Jeffamines) reacted with isocyanates,chloroformates or acyl chlorides or anhydrides.

Additional suitable compatibilizing components are disclosed in U.S.Pat. No. 4,235,985 which is hereby incorporated by reference.

Suitable compatibilizing components may also comprise siliconecontaining macromers which have been modified to include compatibilizingfunctionality as defined above. Such macromers comprise substantialquantities of both Si and HB groups as defined, above, or activehydrogen functionality, such as hydroxyl groups. One class of suitablemacromers include hydroxyl functionalized macromers made by GroupTransfer Polymerization (GTP), or styrene functionalized prepolymers ofhydroxyl functional methacrylates and silicone methacrylates and aredisclosed in U.S. Pat. No. 6,367,929, which is incorporated herein byreference. In the present invention, these macromers are preferably usedwith another compatibilizing component, such as a siloxane containingmonomer. Other macromers, such as those made by radical polymerizationor condensation reaction may also be used independently or incombination with other compatibilizing components so long as the Si tohydrogen molar ratio (OH) of the macromer is less than about 15:1, andpreferably between about 1:1 to about 10:1 or the Si to HB molar ratiois less than about 10:1 and preferably between about 1:1 and about 8:1.However, those of skill in the art will appreciate that includingdifluoromethylene groups will decrease the molar ratio suitable forproviding compatibility.

Suitable monofunctional compatibilizing components are commerciallyavailable from Gelest, Inc. Morrisville, Pa. Suitable multifunctionalcompatibilizing components are commercially available from Gelest, Inc,Morrisville, Pa. or may be made using the procedures disclosed in U.S.Pat. Nos. 5,994,488 and 5,962,548. Suitable PEG type monofunctionalcompatibilizing components may be made using the procedures disclosed inPCT/J P02/02231.

Suitable compatibilizing macromers may be made using the generalprocedure disclosed in U.S. Pat. No. 5,760,100 (material C) or U.S. Pat.No. 6,367,929.

While compatibilizing components comprising hydroxyl functionality havebeen found to be particularly suitable for providing compatible polymersfor biomedical devices, and particulalrly ophthalmic devices, anycompatibilizing component which, when polymerized and/or formed into afinal article is compatible with the selected hydrophilic components maybe used. Compatibilizing components may be selected using the followingmonomer compatibility test. In this test one gram of each ofmono-3-methacryloxypropyl terminated, mono-butyl terminatedpolydimethylsiloxane (mPDMS MW 800-1000) and a monomer to be tested aremixed together in one gram of 3,7-dimethyl-3-octanol at about 20° C. Amixture of 12 weight parts K-90 PVP and 60 weight parts DMA is addeddrop-wise to hydrophobic component solution, with stirring, until thesolution remains cloudy after three minutes of stirring. The mass of theadded blend of PVP and DMA is determined in grams and recorded as themonomer compatibility index. Any compatibilizing component having acompatibility index of greater than 0.5 grams, more preferably greaterthan about 1 grams and most preferably greater than about 1.5 grams willbe suitable for use in this invention. Those of skill in the art willappreciate that the molecular weight of the active compatibilizingcomponent will effect the results of the above test. Compatibilizingcomponents having molecular weights greater than about 800 daltons mayneed to mix for longer periods of time to give representative results.

An “effective amount” of the compatibilizing component of the inventionis the amount needed to compatibilize or dissolve the high molecularweight hydrophilic polymer and the other components of the polymerformulation. Thus, the amount of compatibilizing component will dependin part on the amount of hydrophilic polymer which is used, with morecompatibilizing component being needed to compatibilize higherconcentrations of high molecular weight hydrophilic polymer. Effectiveamounts of compatibilizing component in the polymer formulation includeabout 5% (weight percent, based on the total weight of the reactivecomponents) to about 90%, preferably about 10% to about 80%, mostpreferably, about 20% to about 50%.

In addition to the high molecular weight hydrophilic polymers and thecompatibilizing components of the invention other hydrophilic monomers,oxygen permeability enhancing components, crosslinkers, additives,diluents, polymerization initators may be used to prepare the biomedicaldevices of the invention.

Oxygen Permeable Component

The compositions and devices of the present invention may furthercomprise additional components which provide enhanced oxygenpermeability compared to a conventional hydrogel. Suitable oxygenpermeable components include siloxane containing monomers, macromers andreactive prepolymers, fluorine containing monomers, macromers andreactive prepolymers and carbon-carbon triple bond containing monomers,macromers and reactive prepolmers and combinations thereof, but excludethe compatibilizing component. For the purposes of this invention, theterm macromer will be used to cover both macromers and prepolymers.Preferred oxygen permeable components comprise siloxane containingmonomers, macromers, and mixtures thereof

Suitable siloxane containing monomers include, amide analogs of TRISdescribed in U.S. Pat. No. 4,711,943, vinylcarbamate or carbonateanalogs decribed in U.S. Pat. No. 5,070,215, and monomers contained inU.S. Pat. No. 6,020,445 are useful and these aforementioned patents aswell as any other patents mentioned in this specification are herebyincorporated by reference. More specifically,3-methacryloxypropyltris(trimethylsiloxy)silane (TRIS),monomethacryloxypropyl terminated polydimethylsiloxanes,polydimethylsiloxanes,3-methacryloxypropylbis(trimethylsiloxy)methylsilane,methacryloxypropylpentamethyl disiloxane and combinations thereof areparticularly useful as siloxane containing monomers of the invention.Additional siloxane containing monomers may be present in amounts ofabout 0 to about 75 wt %, more preferably of about 5 and about 60 andmost preferably of about 10 and 40 weight %.

Suitable siloxane containing macromers have a number average molecularweight between about 5,000 and about 15,000 Daltons. Siloxane containingmacromers include materials comprising at least one siloxane group, andpreferably at least one dialkyl siloxane group and more preferably atleast one dimethyl siloxane group. The siloxane containing macromers mayinclude other components such as urethane groups, alkylene or alkyleneoxide groups, polyoxyalkalene groups, arylene groups, alkyl esters,amide groups, carbamate groups, perfluoroalkoxy groups, isocyanategroups, combinations thereof of and the like. A preferred class ofsiloxane containing macromers may be formed via the polymerization ofone or more siloxanes with one or more acrylic or methacrylic materials.Siloxane containing macromers may be formed via group transferpolymerization (“GTP”), free radical polymerization, condensationreactions and the like. The siloxane containing macromers may be formedin one or a series of steps depending on the components selected andusing conditions known in the art. Specific siloxane containingmacromers, and methods for their manufucture, include those disclosed inU.S. Pat. No. 5,760,100 as materials A-D (methacrylate functionalized,silicone-fluoroether urethanes and methacrylate functionalized, siliconeurethanes), and those disclosed in U.S. Pat. No. 6,367,929 (styrenefunctionalized prepolymers of hydroxyl functional methacrylates andsilicone methacrylates), the disclosures of which are incorporatedherein by reference.

Suitable siloxane containing reactive prepolymers include vinylcarbamate functionalized polydimethylsiloxane, which is furtherdisclosed in U.S. Pat. No. 5,070215 and urethane based prepolymerscomprising alternating “hard” segments formed from the reaction of shortchained diols and diisocyantes and “soft” segments formed from arelatively high molecular weight polymer, which is a,w endcapped withtwo active hydrogens. Specific examples of suitable siloxane containingprepolymers, and methods for their manufacture, are disclosed in U.S.Pat. No. 5,034,461, which is incorporated herein by reference.

The hydrogels of the present invention may comprise at least onesiloxane containing macromer. The siloxane containing macromer may bepresent in amounts between about 5 and about 50 weight %, preferablybetween about 10 and about 50 weight % and more preferably between about15 and about 45 weight %, all based upon the total weight of thereactive components.

Suitable fluorine containing monomers include fluorine-containing(meth)acrylates, and more specifically include, for example,fluorine-containing C₂-C₁₂alkyl esters of (meth)acrylic acid such as2,2,2-trifluoroethyl(meth)acrylate,2,2,2,2′,2′,2′-hexafluoroisopropyl(meth)acrylate, 2,2,3,3,4,4,4-heptafluorobutyl(meth)acrylate,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl(meth)acrylate,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl(meth)acrylate andthe like. Fluorine containing macromers and reactive prepolymers includemacromers and prepolymers which include said flurorine containingmonomers.

It has been found that wettability of macromer containing siliconehydrogels may be improved by including at least one hydrophilic polymerand a compatibilizing component. Improved wettability includes adecrease in advancing dynamic contact angle of at least about 10%, andpreferably at least about 20% and in some embodiment a decrease of atleast about 50%. In certain embodiments it may be preferred to usemixtures of siloxane containing monomers or mixtures of siloxanecontaining monomers with siloxane containing macromers or prepolymers.

Hydrophilic Monomers

Additionally, reactive components of the present invention may alsoinclude any hydrophilic monomers used to prepare conventional hydrogels.For example monomers containing acrylic groups (CH₂═CROX, where R ishydrogen or C₁₋₆alkyl an X is O or N) or vinyl groups (—C═CH₂) may beused. Examples of additional hydrophilic monomers areN,N-dimethylacrylamide, 2-hydroxyethyl methacrylate, glycerolmonomethacrylate, 2-hydroxyethyl methacrylamide, polyethyleneglycolmonomethacrylate, methacrylic acid, acrylic acid, N-vinyl pyrrolidone,N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethylformamide, N-vinyl formamide and and combinations thereof.

Aside the additional hydrophilic monomers mentioned above,polyoxyethylene polyols having one or more of the terminal hydroxylgroups replaced with a functional group containing a polymerizabledouble bond may be used. Examples include polyethylene glycol, asdisclosed in U.S. Pat. No. 5,484,863, ethoxylated alkyl glucoside, asdisclosed in U.S. Pat. No. 5,690,953, U.S. Pat. No. 5,304,584, andethoxylated bisphenol A, as disclosed in U.S. Pat. No. 5,565,539,reacted with one or more molar equivalents of an end-capping group suchas isocyanatoethyl methacrylate, methacrylic anhydride, methacryloylchloride, vinylbenzoyl chloride, and the like, produce a polyethylenepolyol having one or more terminal polymerizable olefinic groups bondedto the polyethylene polyol through linking moieties such as carbamate,urea or ester groups.

Still further examples include the hydrophilic vinyl carbonate or vinylcarbamate monomers disclosed in U.S. Pat. No. 5,070,215, the hydrophilicoxazolone monomers disclosed in U.S. Pat. No. 4,910,277, andpolydextran.

The preferred additional hydrophilic monomers are N,N-dimethylacrylamide(DMA), 2-hydroxyethyl methacrylate (HEMA), glycerol methacrylate,2-hydroxyethyl methacrylamide, N-vinylpyrrolidone (NVP),polyethyleneglycol monomethacrylate, methacrylic acid, acrylic acid andcombinations thereof, with hydrophilic monomers comprising DMA beingparticularly preferred. Additional hydrophilic monomers may be presentin amounts of about 0 to about 70 wt %, more preferably of about 5 andabout 60 and most preferably of about 10 and 50 weight %, based upon thetotal weight of the reactive components.

Crosslinkers

Suitable crosslinkers are compounds with two or more polymerizablefunctional groups. The crosslinker may be hydrophilic or hydrophobic andin some embodiments of the present invention mixtures of hydrophilic andhydrophobic crosslinkers have been found to provide silicone hydrogelswith improved optical clarity (reduced haziness compared to a CSI ThinLens®). Examples of suitable hydrophilic crosslinkers include compoundshaving two or more polymerizable functional groups, as well ashydrophilic functional groups such as polyether, amide or hydroxylgroups. Specific examples include TEGDMA (tetraethyleneglycoldimethacrylate), TrEGDMA (triethyleneglycol dimethacrylate),ethyleneglycol dimethacylate (EGDMA), ethylenediamine dimethyacrylamide,glycerol dimethacrylate and combinations thereof Examples of suitablehydrophobic crosslinkers include multifunctional compatibilizingcomponent, multifunctional polyether-polydimethylsiloxane blockcopolymers, combinations thereof and the like. Specific hydrophobiccrosslinkers include acryloxypropyl terminated polydimethylsiloxane(n=10 or 20) (acPDMS), hydroxylacrylate functionalized siloxanemacromer, methacryloxypropyl terminated PDMS, butanediol dimethacrylate,divinyl benzene,1,3-bis(3-methacryloxypropyl)tetrakis(trimethylsiloxy)disiloxane andmixtures thereof. Preferred crosslinkers include TEGDMA, EGDMA, acPDMSand combinations thereof. The amount of hydrophilic crosslinker used isgenerally about 0 to about 2 weight % and preferably from about 0.5 toabout 2 weight % and the amount of hydrophobic crosslinker is about 0 toabout 0 to about 5 weight % based upon the total weight of the reactivecomponents, which can alternatively be referred to in mol% of about 0.01to about 0.2 mmole/gm reactive components, preferably about 0.02 toabout 0.1 and more preferably 0.03 to about 0.6 mmole/gm.

Increasing the level of crosslinker in the final polymer has been foundto reduce the amount of haze. However, as crosslinker concentrationincreases above about 0.15 mmole/gm reactive components modulusincreases above generally desired levels (greater than about 90 psi).Thus, in the present invention the crosslinker composition and amount isselected to provide a crosslinker concentration in the reaction mixtureof between about 1 and about 10 mmoles crosslinker per 100 grams ofreactive components.

Additional components or additives, which are generally known in the artmay also be included. Additives include but are not limited toultra-violet absorbing compounds and monomer, reactive tints,antimicrobial compounds, pigments, photochromic, release agents,combinations thereof and the like.

Diluents

The reactive components (compatibilizing component, hydrophilic polymer,oxygen permeable components, hydrophilic monomers, crosslinker(s) andother components) are mixed and reacted in the absence of water andoptionally, in the presence of at least one diluent to form a reactionmixture. The type and amount of diluent used also effects the propertiesof the resultant polymer and article. The haze and wettability of thefinal article may be improved by selecting relatively hydrophobicdiluents and/or decreasing the concentration of diluent used. Asdiscussed above, increasing the hydrophobicity of the diluent may alsoallow poorly compatible components (as measured by the compatibilitytest) to be processed to form a compatible polymer and article. However,as the diluent becomes more hydrophobic, processing steps necessary toreplace the diluent with water will require the use of solvents otherthan water. This may undesirably increase the complexity and cost of themanufacturing process. Thus, it is important to select a diluent whichprovides the desired compatibility to the components with the necessarylevel of processing convenience. Diluents useful in preparing thedevices of this invention include ethers, esters, alkanes, alkylhalides, silanes, amides, alcohols and combinations thereof. Amides andalcohols are preferred diluents, and secondary and tertiary alcohols aremost preferred alcohol diluents. Examples of ethers useful as diluentsfor this invention include tetrahydrofuran, tripropylene glycol methylether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether,diethylene glycol n-butyl ether, diethylene glycol methyl ether,ethylene glycol phenyl ether, propylene glycol methyl ether, propyleneglycol methyl ether acetate, dipropylene glycol methyl ether acetate,propylene glycol n-propyl ether, dipropylene glycol n-propyl ether,tripropylene glycol n-butyl ether, propylene glycol n-butyl ether,dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether,propylene glycol phenyl ether dipropylene glycol dimetyl ether,polyethylene glycols, polypropylene glycols and mixtures thereof.Examples of esters useful for this invention include ethyl acetate,butyl acetate, amyl acetate, methyl lactate, ethyl lactate, i-propyllactate. Examples of alkyl halides useful as diluents for this inventioninclude methylene chloride. Examples of silanes useful as diluents forthis invention include octamethylcyclotetrasiloxane.

Examples of alcohols useful as diluents for this invention include thosehaving the formula

wherein Where R, R′ and R″ are independently selected from H, a linear,branched or cyclic monovalent alkyl having 1 to 10 carbons which mayoptionally be substituted with one or more groups including halogens,ethers, esters, aryls, aminos, amides, alkenes, alkynes, carboxylicacids, alcohols, aldehydes, ketones or the like, or any two or all threeof R, R and R″ can together bond to form one or more cyclic structures,such as alkyl having 1 to10 carbons which may also be substituted asjust described, with the proviso that no more than one of R, R′ or R″ isH.

It is preferred that R, R′ and R″ are independently selected from H orunsubstituted linear, branched or cyclic alkyl groups having 1 to 7carbons. It is more preferred that R, R′, and R″ are independentlyselected form unsubstituted linear, branched or cyclic alkyl groupshaving 1 to 7 carbons. In certain embodiments, the preferred diluent has4 or more, more preferably 5 or more total carbons, because the highermolecular weight diluents have lower volatility, and lower flammability.When one of the R, R′ and R″ is H, the structure forms a secondaryalcohol. When none of the R, R′ and R″ are H, the structure forms atertiary alcohol. Tertiary alcohols are more preferred than secondaryalcohols. The diluents are preferably inert and easily displaceable bywater when the total number of carbons is five or less.

Examples of useful secondary alcohols include 2-butanol, 2-propanol,menthol, cyclohexanol, cyclopentanol and exonorborneol, 2-pentanol,3-pentonal, 2-hexanol, 3-hexanol, 3-methyl-2-butanol, 2-heptanol,2-octanol, 2-nonanol, 2-decanol, 3-octanol, norborneol, and the like.

Examples of useful tertiary alcohols include tert-butanol, tert-amyl,alcohol, 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol,3-methyl-3-pentanol, 1-methylcyclohexanol, 2-methyl-2-hexanol,3,7-dimethyl-3-octanol, 1-chloro-2-methyl-2-propanol,2-methyl-2-heptanol, 2-methyl-2-octanol, 2-2methyl-2-nonanol,2-methyl-2-decanol, 3-methyl-3-hexanol, 3-methyl-3-heptanol,4-methyl-4-heptanol, 3-methyl-3-octanol, 4-methyl-4-octanol,3-methyl-3-nonanol, 4-methyl-4-nonanol, 3-methyl-3-octanol,3-ethyl-3-hexanol, 3-methyl-3-heptanol, 4-ethyl-4-heptanol,4-propyl-4-heptanol, 4-isopropyl-4-heptanol, 2,4-dimethyl-2-pentanol,1-methylcyclopentanol, 1-ethylcyclopentanol, 1-ethylcyclopentanol,3-hydroxy-3-methyl-1-butene, 4-hydroxy-4-methyl-1-cyclopentanol,2-phenyl-2-propanol, 2-methoxy-2-methyl-2-propanol2,3,4-trimethyl-3-pentanol, 3,7-dimethyl-3-octanol, 2-phenyl-2-butanol,2-methyl-1-phenyl-2-propanol and 3-ethyl-3-pentanol, and the like.

A single alcohol or mixtures of two or more of the above-listed alcoholsor two or more alcohols according to the structure above can be used asthe diluent to make the polymer of this invention.

In certain embodiments, the preferred alcohol diluents are secondary andtertiary alcohols having at least 4 carbons. The more preferred alcoholdiluents include tert-butanol, tert-amyl alcohol, 2-butanol,2-methyl-2-pentanol, 2,3-dimethyl-2-butanol, 3-methyl-3-pentanol,3-ethyl-3-pentanol, 3,7-dimethyl-3-octanol.

Presently, the most preferred diluents are hexanol, heptanol, octanol,nonanol, decanol, tert-butyl alcohol, 3-methyl-3-pentanol, isopropanol,t amyl alcohol, ethyl lactate, methyl lactate, i-propyl lactate,3,7-dimethyl-3-octanol, dimethyl formamide, dimethyl acetamide, dimethylpropionamide, N methyl pyrrolidinone and mixtures thereof. Additionaldiluents useful for this invention are disclosed in U.S. Pat. No.6,020,445, which is incorporated herein by reference.

In one embodiment of the present invention the diluent is water solubleat processing conditions and readily washed out of the lens with waterin a short period of time. Suitable water soluble diluents include1-ethoxy-2-propanol, 1-methyl-2-propanol, t-amyl alcohol, tripropyleneglycol methyl ether, isopropanol, 1-methyl-2-pyrrolidone,N,N-dimethylpropionamide, ethyl lactate, dipropylene glycol methylether, mixtures thereof and the like. The use of a water soluble diluentallows the post molding process to be conducted using water only oraqueous solutions which comprise water as a substantial component.

In one embodiment, the amount of diluent is generally less than about 50weight % of the reaction mixture and preferably less than about 40weight % and more preferably between about 10 and about 30 weight %based upon the total weight of the components of the reaction mixture.

The diluent may also comprise additional components such as releaseagents. Suitable release agents are water soluble and aid in lensdeblocking

The polymerization initiators includes compounds such as laurylperoxide, benzoyl peroxide, isopropyl percarbonate,azobisisobutyronitrile, and the like, that generate free radicals atmoderately elevated temperatures, and photoinitiator systems such asaromatic alpha-hydroxy ketones, alkoxyoxybenzoins, acetophenones, acylphosphine oxides, and a tertiary amine plus a diketone, mixtures thereofand the like. Illustrative examples of photoinitiators are1-hydroxycyclohexyl phenyl ketone,2-hydroxy-2-methyl-1-phenyl-propan-1-one,bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentyl phosphine oxide(DMBAPO), bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (Irgacure819), 2,4,6-trimethylbenzyldiphenyl phosphine oxide,2,4,6-trimethylbenzyoyl diphenylphosphine oxide, benzoin methylester,and a combination of camphorquinone and ethyl4-(N,N-dimethylamino)benzoate. Commercially available visible lightinitiator systems include Irgacure 819, Irgacure 1700, Irgacure 1800,Irgacure 1850 (all from Ciba Specialty Chemicals) and Lucirin TPOinitiator (available from BASF). Commercially available UVphotoinitiators include Darocur 1173 and Darocur 2959 (Ciba SpecialtyChemicals). The initiator is used in the reaction mixture in effectiveamounts to initiate photopolymerization of the reaction mixture, e.g.,from about 0.1 to about 2 parts by weight per 100 parts of reactivemonomer. Polymerization of the reaction mixture can be initiated usingthe appropriate choice of heat or visible or ultraviolet light or othermeans depending on the polymerization initiator used. Alternatively,initiation can be conducted without a photoinitiator using, for example,e-beam. However, when a photoinitiator is used, the preferred initiatoris a combination of 1-hydroxycyclohexyl phenyl ketone andbis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentyl phosphine oxide(DMBAPO), and the preferred method of polymerization initiation isvisible light. The most preferred isbis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (Irgacure 819).

The preferred range of all silicone containing components (oxygenpermeable components and compatibilizing components) is from about 5 to99 weight percent, more preferably about 15 to 90 weight percent, andmost preferably about 25 to about 80 weight percent, based upon thetotal weight of the reactive components. A preferred range ofcompatibilizing components is about 5 to about 90 weight percent,preferably about 10 to about 80, and most preferably about 20 to about50 weight percent. A preferred range of hydrophilic monomer is fromabout 5 to about 80 weight percent, more preferably about 5 to about 60weight percent, and most preferably about 10 to about 50 weight percentof the reactive components in the reaction mixture. A preferred range ofhigh molecular weight hydrophilic polymer is about 1 to about 15 weightpercent, more preferably about 3 to about 15 weight percent, and mostpreferably about 5 to about 12 weight percent. A preferred range ofmacromer is from about 5 to about 50 weight %, preferably from about 10to about 50 weight % and more preferably from about 15 to about 45weight %. All of the foregoing ranges are based upon the total weight ofall reactive components.

A preferred range of diluent is from about 0 to about 70 weight percent,more preferably about 0 to about 50 weight percent, and still morepreferably about 0 to about 40 weight percent and in some embodiments,most preferably between about 10 and about 30 weight percent based uponthe weight of all components in the total reaction mixture. The amountof diluent required varies depending on the nature and relative amountsof the reactive components.

The invention further comprises, consists and consists essentially of asilicone hydrogel, biomedical device, ophthalmic device and contactlenses of the formulations shown below:

Wt % components CC HMWHP ASCM SCM HM  5-90 1-15, 3-15 or 5-12 0 0 010-80 1-15, 3-15 or 5-12 0 0 0 15-55 1-15, 3-15 or 5-12 0 0 0  5-901-15, 3-15 or 5-12  5-50 10-80 1-15, 3-15 or 5-12 10-50 15-55 1-15, 3-15or 5-12 15-45  5-90 1-15, 3-15 or 5-12 0-80, 5-60 5-50; 10-50; 0-70,5-60 or or 10-40 15-45 10-50 10-80 1-15, 3-15 or 5-12 0-80, 5-60 5-50;10-50; 0-70, 5-60 or or 10-40 15-45 10-50 15-55 1-15, 3-15 or 5-12 0-80,5-60 5-50; 10-50; 0-70, 5-60 or or 10-40 15-45 10-50 CC iscompatibilizing component HMWHP is high molecular weight hydrophilicpolymer ASCM is additional siloxane containing monomer HM is hydrophilicmonomer SCM is a siloxane containing macromer

Thus, the present invention includes silicone hydrogel, biomedicaldevice, ophthalmic device and contact lenses having each of thecomposition listed in the table, which describes 261 possiblecompositional ranges. Each of the ranges listed above is prefaced by theword “about”. The foregoing range combinations are presented with theproviso that the listed components, and any additional components add upto 100 weight %.

In a preferred embodiment, the reactive components comprise about 28 wt.% SiGMA; about 31 wt. % 800-1000 MW monomethacryloxypropyl terminatedmono-n-butyl terminated polydimethylsiloxane, “mPDMS”, about 24 wt. %N,N-dimethylacrylamide, “DMA”, about 6 wt. % 2-hydroxyethyl methacryate,“HEMA”, about 1.5 wt % tetraethyleneglycoldimethacrylate, “TEGDMA”,about 7 wt. % polyvinylpyrrolidone, “K-90 PVP”; with the balancecomprising minor amounts of additives and photoinitiators. Thepolymerization is most preferably conducted in the presence of about 23%(weight % of the combined monomers and diluent blend)3,7-dimethyl-3-octanol diluent.

In a second preferred embodiment the reactive components comprise about30 wt. % SiGMA, about 23 wt. % mPDMS, about 31 wt % DMA, about 0.5 toabout 1 wt. % ethyleneglycoldimethacrylate, “EGDMA”, about 6 wt. % K-90PVP; and about 7.5 wt % HEMA, with the balance comprising minor amountsof additives and photoinitiators. The polymerization is most preferablyconducted in the presence of tert-amyl-alcohol as a diluent comprisingabout 29 weight percent of the reaction mixture. The diluent may alsocomprise about 11 weight % low molecular weight PVP (less than about5,000 and preferably less than about 3,000 M_(n).

In a third preferred embodiment, the reactive components comprise about11-18 wt % macromer (the GTP reaction product of about 24 wt. % HEMA;about 3wt % MMA; about 33wt. %methacryloxypropyltris(trimethylsiloxy)silane and about 32wt. %mono-methacryloxypropyl terminated mono-butyl terminatedpolydimethylsiloxane functionalized with 8 wt %3-isopropenyl-α,α-dimethylbenzyl isocyanate); about 18-30 wt. % mPDMS,about 2-10 wt % acPDMS, about 27-33 wt. % DMA, about 13-15 wt. % TRIS,about 2-5 wt. % HEMA, and about 5-7 wt. % K-90 PVP; with the balancecomprising minor amounts of additives and photoinitiators. Thepolymerization is most preferably conducted in the presence of 25-30%(weight % of the combined monomers and diluent blend) a diluentcomprising 3,7-dimethyl-3-octanol.

In a fourth preferred embodiment, the reactive components comprisebetween about 15 to about 40 wt. % macromer (formed from perfluoroetherhaving a mean molecular weight of about 1030 g/mol and α,ω-hydroxypropyl-terminated polydimethylsiloxane having a mean molecularweight of about 2000 g/mol, isophorone diisocyanate and isocyanatoethylmethacrylate); about 40 to about 52% SiGMA, about 0 to about 5 wt %3-tris(trimethylsiloxy)silylpropyl methacrylate, “TRIS”, about 22 toabout 32 wt. % DMA, about 3 about 8 wt % K-90 PVP with the balancecomprising minor amounts of additives and photoinitiators. Thepolymerization is most preferably conducted in the presence of about 15to about 40, and preferably between about 20 and about 40% (weight % ofthe combined monomers and diluent blend), diluent, which may, in someemobodiments preferably be ethanol, 3,7-dimethyl-3-octanol.

Processing

The biomedical devices of the invention are prepared by mixing the highmolecular weight hydrophilic polymer, the compatibilizing component,plus one or more of the following: the oxygen permeability enhancingcomponent, the hydrophilic monomers, the additives (“reactivecomponents”), and the diluents (“reaction mixture”), with apolymerization initator and curing by appropriate conditions to form aproduct that can be subsequently formed into the appropriate shape bylathing, cutting and the like. Alternatively, the reaction mixture maybe placed in a mold and subsequently cured into the appropriate article.

Various processes are known for curing the reaction mixture in theproduction of contact lenses, including spincasting and static casting.Spincasting methods are disclosed in U.S. Pat. Nos. 3,408,429 and3,660,545, and static casting methods are disclosed in U.S. Pat. Nos.4,113,224 and 4,197,266. The preferred method for producing contactlenses comprising the polymer of this invention is by the direct moldingof the silicone hydrogels, which is economical, and enables precisecontrol over the final shape of the hydrated lens. For this method, thereaction mixture is placed in a mold having the shape of the finaldesired silicone hydrogel, i.e., water-swollen polymer, and the reactionmixture is subjected to conditions whereby the monomers polymerize, tothereby produce a polymer/diluent mixture in the shape of the finaldesired product. Then, this polymer/diluent mixture is treated with asolvent to remove the diluent and ultimately replace it with water,producing a silicone hydrogel having a final size and shape which arequite similar to the size and shape of the original moldedpolymer/diluent article. This method can be used to form contact lensesand is further described in U.S. Pat. Nos. 4,495,313; 4,680,336;4,889,664; and 5,039,459, incorporated herein by reference.

Curing

Yet another feature of the present invention is a process for curingsilicone hydrogel formulations to provide enhanced wettability. It hasbeen found that the gel time for a silicone hydrogel may be used toselect cure conditions which provide a wettable ophthalmic device, andspecifically a contact lens. The gel time is the time at which acrosslinked polymer network is formed, resulting in the viscosity of thecuring reaction mixture approaching infinity and the reaction mixturebecoming non-fluid. The gel point occurs at a specific degree ofconversion, independent of reaction conditions, and therefore can beused as an indicator of the rate of the reaction. It has been foundthat, for a given reaction mixture, the gel time may be used todetermine cure conditions which impart desirable wettability. Thus, in aprocess of the present invention, the reaction mixture is cured at orabove a gel time that provides improved wettability, or more preferablysufficient wettability for the resulting device to be used without ahydrophilic coating or surface treatment (“minimum gel time”).Preferably improved wettability is a decrease in advancing dynamiccontact angle of at least 10% compared to formulation with no highmolecular weight polymer. Longer gel times are preferred as they provideimproved wettability and increased processing flexibility.

Gel times will vary for different silicone hydrogel formulations. Cureconditions also effect gel time. For example the concentration ofcrosslinker will impact gel time, increasing crosslinker concentrationsdecreases gel time. Increasing the intensity of the radiation (forphotopolymerization) or temperature (for thermal polymerization), theefficiency of initiation (either by selecting a more efficient initiatoror irradiation source, or an initiator which absorbs more strongly inthe selected irradiation range) will also decrease gel time. Temperatureand diluent type and concentration also effect gel time in waysunderstood by those of skill in the art.

The minimum gel time may be determined by selecting a given formulation,varying one of the above factors and measuring the gel time and contactangles. The minimum gel time is the point above which the resulting lensis generally wettable. Below the minimum gel time the lens is generallynot wettable. For a contact lens “generally wettable” is a lens whichdisplays an advancing dynamic contact angle of less than about 70 andpreferably less than about 60° or a contact lens which displays a tearfilm break up time equal to or better than an ACUVUE® lens. Thus, thoseof skill in the art will appreciate that minimum gel point as definedherein may be a range, taking into consideration statisticalexperimental variability.

In certain embodiments using visible light irradiation minimum gel timesof at least about 30, preferably greater than about 35, and morepreferably greater than about 40 seconds have been found to beadvantageous.

Curing may be conducted using heat, ionizing or actinic radiation, forexample electron beams, Xrays, UV or visible light, ie. electromagneticradiation or particle radiation having a wavelength in the range of fromabout 150 to about 800 nm. Preferable radiation sources include UV orvisible light having a wavelength of about 250 to about 700 nm. Suitableradiation sources include UV lamps, fluorescent lamps, incandescentlamps, mercury vapor lamps, and sunlight. In embodiments where a UVabsorbing compound is included in the reaction mixture (for example, asa UV block or photochromic) curing is conducting by means other than UVirradiation (such as by visible light or heat). In a preferredembodiment the radiation source is selected from UVA (about 315-about400 nm), UVB (about 280-about 315) or visible light (about 400-about 450nm). In another preferred embodiment, the reaction mixture includes a UVabsorbing compound, is cured using visible light. In many embodiments itwill be useful to cure the reaction mixture at low intensity to achievethe desired minimum gel time. As used herein the term “low intensity”means those between about 0.1 mW/cm² to about 6 mW/cm² and preferablybetween about 1 mW/cm² and 3 mW/cm². The cure time is long, generallymore than about 1 minute and preferably between about 1 and about 60minutes and still more preferably between about 1 and about 30 minutesThis slow, low intensity cure is one way to provide the desired minimumgel times and produce ophthalmic devices which display good wettability.

Initiator concentration also effects gel time. Accordingly, in someembodiments it is preferred to have relatively low amounts ofphotoinitiator, generally 1% or less and preferably 0.5% or less.

The temperature at which the reaction mixture is cured is alsoimportant. As the temperature is increased above ambient the haze of theresulting polymer decreases. Temperatures effective to reduce hazeinclude temperatures at which the haze for the resulting lens isdecreased by at least about 20% as compared to a lens of the samecomposition made at 25° C. Thus, suitable cure temperatures includethose greater than about 25° C., preferably those between about 25° C.and 70° C. and more preferably those between about 40° C. and 70° C. Theprecise set of cure conditions (temperature, intensity and time) willdepend upon the components of lens material selected and, with referenceto the teaching herein, are within the skill of one of ordinary skill inthe art to determine. Cure may be conducted in one or a muptiplicity ofcure zones.

The cure conditions must be sufficient to form a polymer network fromthe reaction mixture. The resulting polymer network is swollen with thediluent and has the form of the mold cavity.

Deblocking

After the lenses have been cured they must be removed from the mold.Unfortunately, the silicone components used in the lens formulationrender the finished lenses “sticky” and difficult to release from thelens molds. Lenses can be deblocked (removed from the mold half or toolsupporting the lens) using a solvent, such as an organic solvent.However, in one embodiment of the present invention at least one lowmolecular weight hydrophilic polymer is added to the reaction mixture,the reaction mixture is formed into the desired article, cured anddeblocked in water or an aqueous solution comprising, consistingessentially of and consisting of a small amount of surfactant. The lowmolecular weight hydrophilic polymer can be any polymer having astructure as defined for a high molecular weight polymer, but with amolecular weight such that the low molecular weight hydrophilic polymerextracts or leaches from the lens under deblocking conditions to assistin lens release from the mold. Suitable molecular weights include thoseless than about 40,000 Daltons and preferably less than about 20,000Daltons. Those of skill in the art will appreciate that the foregoingmolecular weights are averages, and that some amount of material havinga molecular weight higher than the given averages may be suitable, solong as the average molecular weight is within the specified range.Preferably the low molecular weight polymer is selected from watersoluble polyamides, lactams and polyethylene glycols, and mixturesthereof and more preferably poly-vinylpyrrolidone, polyethylene glycols,poly 2 ethyl-2-oxazoline (available from Plymer Chemistry Innovations,Tuscon, Ariz.), polymethacrylic acid, poly(1-lactic acid),polycaprolactam, polycaprolactone, polycaprolactone diol, polyvinylalcohol, polyhema, polyacrylic acid, poly(1-glycerol methacrylate),poly(2-ethyl-2-oxazoline), poly(2-hydroxypropyl methacrylate),poly(2-vinylpyridine N-oxide), polyacrylamide, polymethacrylamide andthe like.

The low molecular weight hydrophilic polymer may be used in amounts upto about 20 wt. % and preferably in amounts between about 5 and about 20wt % of the reactive components.

Suitable surfactants include non-ionic surfactants including betaines,amine oxides, combinations thereof and the like. Examples of suitablesurfactants include TWEEN® (ICI), DOE 120 (Amerchol/Union Carbide andthe like. The surfactants may be used in amounts up to about 10,000 ppm,preferably between about 25 ppm and about 1500 ppm and more preferablybetween about 100 and about 1200 ppm.

Suitable release agents are low molecular weight, and include1-methyl-4-piperidone, 3-morpholino-1,2-propanediol,tetrahydro-2H-pyran-4-ol, glycerol formal, ethyl-4-oxo-1-piperidinecarboxylate, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone and1-(2-hydroxyethyl)-2-pyrrolidone

Lenses made from reaction mixtures without low molecular weighthydrophilic polymer may be deblocked in an aqueous solution comprisingat least one organic solvent. Suitable organic solvents are hydrophobic,but miscible with water. Alcohols, ethers and the like are suitable,more specifically primary alcohols and more specifically isopropylalcohol, DPMA, TPM, DPM, methanol, ethanol, propanol and mixturesthereof being suitable examples.

Suitable deblocking temperatures range from about ambient to about 100°C., preferably between about 70° C. and 95° C., with higher temperaturesproviding quicker deblocking times. Agitation, such as by sonication,may also be used to decrease deblocking times. Other means known in theart, such as vacuum nozzles may also be used to remove the lenses fromthe molds.

Diluent Replacement/Hydration

Typically after curing the reaction mixture, the resulting polymer istreated with a solvent to remove the diluent (if used), unreactedcomponents, byproducts, and the like and hydrate the polymer to form thehydrogel. Alternatively, depending on the solubility characteristics ofthe hydrogel's components, the solvent initially used can be an organicliquid such as ethanol, methanol, isopropanol, TPM, DPM, PEGs, PPGs,glycerol, mixtures thereof, or a mixture of one or more such organicliquids with water, followed by extraction with pure water (orphysiological saline). The organic liquid may also be used as a“pre-soak”. After demolding, lenses may be briefly soaked (times up toabout 30 minutes, preferably between about 5 and about 30 minutes) inthe organic liquid or a mixture of organic liquid and water. After thepre-soak, the lens may be further hydrated using aqueous extractionsolvents.

In some embodiments, the preferred process uses an extraction solventthat is predominately water, preferably greater than 90% water, morepreferably greater than 97% water. Other components may includes saltssuch as sodium chloride, sodium borate boric acid, DPM, TPM, ethanol orisopropanol. Lenses are generally released from the molds into thisextraction solvent, optionally with stirring or a continuous flow of theextraction solvent over the lenses. This process can be conducted attemperatures from 2 to 121° C., preferably from 20 to 98° C. The processcan be conducted at elevated pressures, particularly when usingtemperatures in excess of 100° C., but is more typically conducted atambient pressures. It is possible to deblock the lenses into onesolution (for example containing some release aid) and then transferthem into another (for example the final packing solution), although itmay also be possible to deblock the lenses into the same solution inwhich they are packaged. The treatment of lenses with this extractionsolvent may be conducted for a period of from about 30 seconds to about3 days, preferably between about 5 and about 30 minutes. The selectedhydration solution may additional comprise small amounts of additivessuch as surfactants and/or release aids. Suitable surfactants includeinclude non-ionic surfactants, such as betaines and amine oxides.Specific surfactants include TWEEN 80 (available from Amerchol), DOE 120(available from Union Carbide), Pluronics, methyl cellulose, mixturesthereof and the like and may be added in amounts between about 0.01weight % and about 5% based upon total weight of hydration solutionused.

In one embodiment the lenses may be hydrated using a “step down” method,where the solvent is replaced in steps over the hydration process.Suitable step down processes have at least two, at least three and insome embodiments at least four steps, where a percentage of the solventis replaced with water.

The silicone hydrogels after hydration of the polymers preferablycomprise about 10 to about 60 weight percent water, more preferablyabout 20 to about 55 weight percent water, and most preferably about 25to about 50 weight percent water of the total weight of the siliconehydrogel. Further details on the methods of producing silicone hydrogelcontact lenses are disclosed in U.S. Pat. Nos. 4,495,313; 4,680,336;4,889,664; and 5,039,459, which are hereby incorporated by reference.

The cured biomedical device of the present invention displays excellentresistance to fouling in vivo, even without a coating. When thebiomedical device is an ophthalmic device, resistance to biofouling maybe measured by measuring the amount of surface deposits on the lensduring the wear period, often referred to as “lipid deposits”.

Lens surface deposits are measured as follows: Lenses were put on humaneyes and evaluated after 30 minutes and one week of wear using a slitlamp. During the evaluation the patient is asked to blink several timesand the lenses are manually “pushed” in order to differentiate betweendeposits and back surface trapped debris. Front and back surfacedeposits are graded as being discrete (i.e. jelly bumps) or filmy. Frontsurface deposits give a bright reflection while back surface deposits donot. Deposits are differentiated from back surface trapped debris duringa blink or a push-up test. The deposits will move while the back surfacetrapped debris will remain still. The deposits are graded into fivecategories based upon the percentage of the lens surface which iseffected: none (<about 1%), slight (about 1 to about 5%), mild (about 6%to about 15%), moderate (about 16% to about 25%) and severe (greaterthan about 25%). A 10% difference between the categories is consideredclinically significant.

The ophthalmic devices of the present invention also display low haze,good wettability and modulus.

Haze is measured by placing test lenses in saline in a clear cell abovea black background, illuminating from below with a fiber optic lamp atan angle 66° normal to the lens cell, and capturing an image of the lensfrom above with a video camera. The background-subtracted scatteredlight image was quantitatively analyzed, by integrating over the central10 mm of the lens, and then compared to a −1.00 diopter CSI Thin Lens®,which is arbitrarily set at a haze value of 100, with no lens set as ahaze value of 0.

Wettability is measured by measuring the contact angle or DCA, typicallywith borate buffered saline, using a Wilhelmy balance at 23° C. Thewetting force between the lens surface and borate buffered saline ismeasured using a Wilhelmy microbalance while the sample is beingimmersed into or pulled out of the saline. The following equation isused

F=2γp cos θ or θ=cos⁻¹(F/2γp)

where F is the wetting force, y is the surface tension of the probeliquid, p is the perimeter of the sample at the meniscus and θ is thecontact angle. Typically, two contact angles are obtained from a dynamicwetting experiment—advancing contact angle and receding contact angle.Advancing contact angle is obtained from the portion of the wettingexperiment where the sample is being immersed into the probe liquid. Atleast 4 lenses of each composition are measured and the values reportedherein.

However, DCA is not always a good predictor of wettability on eye. Thepre-lens tear film non-invasive break-up time (PLTF-NIBUT) is onemeasure of in vivo or “clinical” lens wettability. The PLTF-NIBUT ismeasured using a slit lamp and a circular fluorescent tearscope fornoninvasive viewing of the tearfilm (Keeler Tearscope Plus). The timeelapsed between the eye opening after a blink and the appearance of thefirst dark spot within the tear film on the front surface of a contactlens is recorded as PLTF-NIBUT. The

PLTF-NIBUT was measured 30-minutes after the lenses were placed on eyeand after one week. Three measurements were taken at each time intervaland were averaged into one reading. The PLTF-NIBUT was measured on botheyes, beginning with the right eye and then the left eye.

Movement is measured using the “push up” test. The patient's eyes are inthe primary gaze position. The push-up test is a gentle digital push ofthe lens upwards using the lower lid. The resistance of the lens toupward movement is judged and graded according to the following scale: 1(excessive, unacceptable movement), 2 (moderate, but acceptablemovement), 3 (optimal movement), 4 (minimal, but acceptable movement), 5(insufficient, unacceptable movement).

The lenses of the present invention display moduli of at least about 30psi, preferably between about 30 and about 90 psi, and more preferablybetween about 40 and about 70 psi. Modulus is measured by using thecrosshead of a constant rate of movement type tensile testing machineequipped with a load cell that is lowered to the initial gauge height. Asuitable testing machine includes an Instron model 1122. A dog-boneshaped sample having a 0.522 inch length, 0.276 inch “ear” width and0.213 inch “neck” width is loaded into the grips and elongated at aconstant rate of strain of 2 in/min. until it breaks. The initial gaugelength of the sample (Lo) and sample length at break (Lf) are measured.Twelve specimens of each composition are measured and the average isreported. Tensile modulus is measured at the initial linear portion ofthe stress/strain curve.

The contact lenses prepared by this invention have O₂ Dk values betweenabout 40 and about 300 barrer, determined by the polarographic method.Lenses are positioned on the sensor then covered on the upper side witha mesh support. The lens is exposed to an atmosphere of humified 2.1%O₂. The oxygen that diffuses through the lens is measured using apolarographic oxygen sensor consisting of a 4 mm diameter gold cathodeand a silver ring anode. The reference values are those measured oncommercially available contact lenses using this method. Balafilcon Alenses available from Bausch & Lomb give a measurement of approx. 79barrer. Etafilcon lenses give a measurement of 20 to 25 barrer. (1barrer=10⁻¹⁰ (cm³ of gas×cm²)/(cm³ of polymer×s×cm Hg).

Gel time was measured using the following method. Thephoto-polymerization reaction was monitored with an ATS StressTechrheometer equipped with a photo-curing accessory, which consists of atemperature-controlled cell with a quartz lower plate and an aluminumupper plate, and a radiation delivery system equipped with a bandpassfilter. The radiation, which originates at a Novacure mercury arc lampequipped with an iris and computer-controlled shutter, was delivered tothe quartz plate in the rheometer via a liquid light guide. The filterwas a 420 nm (20 nm FWHM) bandpass filter, which simulates the lightemitted from a TL03 bulb. The intensity of the radiation, measured atthe surface of the quartz window with an IL1400A radiometer, wascontrolled to ±0.02 mW/cm2 with an iris. The temperature was controlledat 45±0.1° C. After approximately 1 mL of the de-gassed reactive mixturewas placed on the lower plate of the rheometer, the 25 mm diameter upperplate was lowered to 0.500±0.001 mm above the lower plate, where it washeld until after the reaction reached the gel point.

The sample was allowed to reach thermal equilibrium (˜4 minutes,determined by the leveling-off of the steady shear viscosity) before thelamp shutter was opened and the reaction begun. During this time whilethe sample was reaching thermal equilibrium, the sample chamber waspurged with nitrogen gas at a rate of 400 sccm. During the reaction therheometer continuously monitored the strain resulting from an applieddynamic stress (fast oscillation mode), where time segments of less thana complete cycle were used to calculate the strain at the appliedprogrammable stress. The computer calculated the dynamic shear modulus(G′), loss modulus (G″), and viscosity (v*), as a function of exposuretime. As the reaction proceeded the shear modulus increased from <1 Pato >0.1 MPa, and tan δ(=G″/G′) dropped from near infinity to lessthan 1. For measurements made herein the gel time is the time at whichtan δ equals 1 (the crossover point when G′=G″). At the time that G′reaches 100 Pa (shortly after the gel point), the restriction on theupper plate was removed so that the gap between the upper and lowerplates can change as the reactive monomer mix shrinks during cure.

It will be appreciated that all of the tests specified above have acertain amount of inherent test error. Accordingly, results reportedherein are not to be taken as absolute numbers, but numerical rangesbased upon the precision of the particular test.

In order to illustrate the invention the following examples areincluded. These examples do not limit the invention. They are meant onlyto suggest a method of practicing the invention. Those knowledgeable incontact lenses as well as other specialties may find other methods ofpracticing the invention. However, those methods are deemed to be withinthe scope of this invention.

Examples

The following abbreviations are used in the examples below:

-   -   SiGMA 2-propenoic acid,        2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[trimethylsilyl)oxy]disiloxanyl]propoxy]propyl        ester    -   DMA N,N-dimethylacrylamide    -   HEMA 2-hydroxyethyl methacrylate    -   mPDMS 800-1000 MW (M_(n)) monomethacryloxypropyl terminated        mono-n-butyl terminated polydimethylsiloxane    -   Norbloc        2-(2′-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole    -   CGI 1850 1:1 (wgt) blend of 1-hydroxycyclohexyl phenyl ketone        and bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentyl phosphine        oxide    -   PVP poly(N-vinyl pyrrolidone) (K value 90)    -   Blue HEMA the reaction product of Reactive Blue 4 and HEMA, as        described in Example 4 of U.S. Pat. No. 5,944,853    -   IPA isopropyl alcohol    -   D3O 3,7-dimethyl-3-octanol    -   mPDMS-OH mono-(3-methacryloxy-2-hydroxypropyloxy)propyl        terminated, mono-butyl terminated polydimethylsiloxane (MW 1100)    -   TEGDMA tetraethyleneglycol dimethacrylate    -   TrEGDMA triethyleneglycol dimethacrylate    -   TRIS 3-methacryloxypropyltris(trimethylsiloxy)silane    -   MPD 3-methacryloxypropyl(pentamethyldisiloxane)    -   MBM 3-methacryloxypropylbis(trimethylsiloxy)methylsilane    -   AcPDMS bis-3-methacryloxy-2-hydroxypropyloxypropyl        polydimethylsiloxane    -   TRIS-HEMA 2-trimethylsiloxyethyl methacrylate    -   MMA methyl methacrylate    -   THF tetrahydrofuran    -   TBACB tetrabutylammonium 3-chlorobenzoate    -   TMI 3-isopropenyl- -dimethylbenzyl isocyanate    -   IPL isopropyl lactate    -   CGI 819 2,4,6-trimethylbenzyldiphenyl phosphine oxide

Throughout the Examples intensity is measured using an IL 1400Aradiometer, using an XRL 140A sensor.

Examples 1-10

The reaction components and diluent (D30) listed in Table 1 were mixedtogether with stirring or rolling for at least about 3 hours at 23° C.,until all components were dissolved. The reactive components arereported as weight percent of all reactive components and the diluent isweight percent of reaction mixture. The reaction mixture was placed intothermoplastic contact lens molds (made from Topas® copolymers ofethylene and norbornene obtained from Ticona Polymers), and irradiatedusing Philips TL 20W/03T fluorescent bulbs at 45° C. for about 20minutes N₂. The molds were opened and lenses were extracted into a 50:50(wt) solution of IPA and H₂O, and soaked in IPA at ambient temperaturefor about 15 hours to remove residual diluent and monomers, placed intodeionized H₂O for about 30 minutes, then equilibrated in borate bufferedsaline for at least about 24 hours and autoclaved at 122° C. for 30minutes. The properties of the resulting lenses are shown in Table 1.

TABLE 1 EX. # Comp. 1 2 3 4 5 6 7 8 9 10 SiGMA 28 30 28.6 28 31 32 2939.4 20 68 PVP (K90) 7 10 7.1 7 7 7 6 6.7 3 7 DMA 23.5 17 24.5 23.5 2020 24 16.4 37 22 MPDMS 31 32 0 31 31 34 31 29.8 15 0 TRIS 0 0 0 0 0 0 00 15 0 HEMA 6 6 6.1 6 6.5 3 5.5 2.9 8 0 Norbloc 2 2 0 2.0 2 2 2 1.9 0 0CGI 1850 0.98 1 1.02 1 1 1 1 1 1 0 TEGDMA 1.5 2 1.02 1.5 1.5 1 1.5 1.9 02 TrEGDMA 0 0 0 0 0 0 0 0 1 0 Blue HEMA 0.02 0 0 0 0 0 0 0 0 0 mPDMS-OH0 0 31.6 0 0 0 0 0 0 0 Darocur 0 0 0 0 0 0 0 0 0 1 1173 D30 % 23 26 1723 23 29 32 28 17 27 Properties % EWC¹ 36 33 39 40 36 37 39 25 48 29Modulus 68 78 112 61 67 50 66 92 43 173 (psi) % Elongation 301 250 147294 281 308 245 258 364 283 DCA² 62 55 58 64 72 65 61 55 92 72(advancing) Dk³ 103 111 101 131 110 132 106 140 64 76 (edge corrected)¹Equilibrium water content ²Dynamic contact angle, measured withphysiological borate-buffered saline using a Wilhelmy balance. ³Oxygenpermeability, edge corrected, in Barrers.

The results of Examples 1-10 show that the reaction mixture componentsand their amounts may be varied substantially, while still providinguncoated lenses having an excellent balance of mechanical properties andwettability. The contact angle (DCA) of Example 9 may be too high toform a lens that would be clinically wettable, and the modulus may belower than desired to provide a mechanically robust lens. Example 9contained the lowest concentration of SiGMA (20%). Because the SiGMA hadbeen reduced, less PVP could be added to the formulation and stillprovide a compatible reaction mixture. Thus, these examples show thatSiGMA is effective in compatibilizing PVP and that when sufficient SiGMAand PVP are present lenses with desirable wettability and othermechanical properties can be made without any form of surfacemodification.

Example 11

Lenses having the formulation of Example 1 were remade, withoutcontrolling cure intensity. The mechanical properties are reported inTable 2, below. These lenses were clinically evaluated using ACUVUE® 2lenses as controls. The test lenses were worn in one eye and an ACUVUE®2lens was worn on the contralateral eye. The lenses were worn by 6patients in a daily wear mode (nightly removal) for a period of oneweek. At one week the PLTF-NIBUT was 3.6 (±3.0) seconds compared to 5.8(±2.5) seconds for ACUVUE® 2 lenses. The front surface deposition wasgraded none to slight for 50% of the test lenses and 100% for thecontrol lenses. The movement was acceptable for both test and controllenses.

Example 12

Example 11 was repeated except that the cure intensity was reduced to1.0 mW/cm². The mechanical properties are reported in Table 2, below.These lenses were clinically evaluated using ACUVUE® 2 lenses ascontrols. The test lenses were worn by 15 patients in a daily wear mode(nightly removal), in one eye for a period of one week and an ACUVUE® 2lens was worn in the contralateral eye. At one week the PLTF-NIBUT was8.2 (±1.7) seconds compared to 6.9 (±1.5) seconds for ACUVUE® 2 lenses.The front surface deposition was graded none to slight for all of thepatients for both test and control lenses. The movement was acceptablefor both test and control lenses.

TABLE 2 Ex.# 1 11 12 % EWC 36 36 36 Modulus (psi) 68 74 87 Elongation301 315 223 DCA 62 77 56 Dk 103 127 102

Generally the mechanical properties for Examples 1, 11 and 12 areconsistent results for multiple runs of the same material. However, theclinical results for Examples 11 (uncontrolled cure intensity) and 12(low, controlled cure intensity) are substantially different. The on eyewettability after one week of wear for Example 11 (measured byPLTF-NIBUT) was worse that the ACUVUE® 2 lenses (3.6 v. 5.8) and halfthe lenses had more than slight surface depositions. The Example 12lenses (controlled, low intensity cure) displayed significantly improvedon-eye wettability, which was measurably better than ACUVUE® 2 lenses(8.2 v. 6.9) and no surface depositions. Thus, using a low, controlledcure provides an uncoated lens having on-eye wettability which is asgood as, and in some cases better than conventional hydrogel lenses.

Examples 13-17

Reaction mixtures described in Table 3 and containing low or nocompatibilizing component (in these Examples SiGMA) were mixed withconstant stirring at room temperature for 16 hours. Even after 16 hourseach of the reaction mixtures remained cloudy and some containedprecipitates. Accordingly, these reaction mixtures could not be used toproduce lenses.

TABLE 3 Ex. # Composition 13 14 15 16 17 SiGMA 0 0 0 10 20 PVP (K90) 1212 10 8.0 8.0 DMA 10 10 8.3 19 19 MPDMS 37 37 30.8 35 28 TRIS 14 14 11.717 14 HEMA 25 25 37.5 8.0 8.0 Norbloc 0 0 0 0 0 CGI 1850 0 0 0 0 0TEGDMA 1.0 1.0 0.83 2.0 2.0 TrEGDMA 0 0 0 0 0 Blue HEMA 0 0 0 0 0mPDMS-OH 0 0 0 0 0 Darocur 1.0 1.0 0.83 1.0 1.0 1173 D30 % 23 31 31 2727

Examples 13 through 15 show that reaction mixtures without anycompatibilizing component (SiGMA or mPDMS-OH) are incompatible, and notsuitable for making contact lenses. Examples 16 and 17 show thatconcentrations of compatibilizing component less than about 20 weight %are insufficient to compatibilize signifincant amounts of high molecularweight PVP. However, comparing Example 17 to Example 9, lesser amountsof high molecular weight PVP (3 weight %) can be included and still forma compatible reaction mixture.

Examples 18-26

A solution of 1.00 gram of D3O, 1.00 gram of mPDMS and 1.00 gram of TRISwas placed in a glass vial (Ex. 18). As the blend was rapidly stirred atabout 20 to 23° C. with a magnetic stir bar, a solution of 12 parts (wt)PVP (K90) and 60 parts DMA was added dropwise until the solutionremained cloudy after 3 minutes of stirring. The mass of the addedDMA/PVP blend was determined in grams and reported as the “monomercompatibility index”. This test was repeated using SiGMA (Ex. 19), MBM(Ex. 20), MPD (Ex. 21), acPDMS, where n=10 (Ex. 22), acPDMS where n=20(Ex. 23), iSiGMA-3Me (Ex. 24) and TRIS2-HOEOP2 (Ex. 25) as test siliconemonomers in place of TRIS.

TABLE 4 Monomer Test silicone- compatibility Ex. # containing monomerindex Si:OH 18 SiGMA 1.8   3:1 19 TRIS 0.07   4:0 20 MBM 0.09   3:0 21MPD 0.05   2:0 22 acPDMS (n = 10)* 1.9  11:2 23 acPDMS (n = 20)* 1  21:224 ISiMAA-3Me 0.15   4:0 25 TRIS2-HOEOP2 0.11   3:2 26 MPDMS-OH 0.64~11:2 Doug - should we try mPDMS-OH and see what that number is?Structures for acPDMS, iSiGMA-3Me and TRIS2-HOEOP2 are shown below.acPDMS (n averages 10 or 20):

TRIS2-HOEOP2

iSiMAA3-Me

The results, shown in Table 4, show that SiGMA, acPDMS (where n=10 and20) and mPDMS-OH more readily incorporate into a blend of a diluent,another silicone containing monomer, a hydrophilic monomer, and an highmolecular weight polymer (PVP) than alternative silicone-containingmonomers. Thus, compatibilizing silicone containing monomers having acompatibility index of greater than about 0.5 are useful forcompatibilizing high molecular weight hydrophilic polymers like PVP.

Example 27-35

Lenses were made using the reaction mixture formulation of Example 1.The plastic contact lens molds (made from Topas® copolymers of ethyleneand norbornene obtained from Ticona Polymers) were stored overnight innitrogen (<0.5% O₂) before use. Each mold was dosed with 75 μl reactionmixture. Molds were closed and lenses photocured using the times andcure intensities indicated in Table 5. Lenses were formed by irradiationof the monomer mix using visible light fluorescent bulbs, curing at 45°C. The intensity was varied by using a variable balast or light filters,in two steps of varied intensity and cure time. The step 2 time wasselected to provide the same total irradiation energy (about 830 mJ/cm²)for each sample.

The finished lenses were demolded use a 60:40 mixture of isopropylalcohol/DI water. The lenses were transferred to a jar containing 300 g100% isopropyl alcohol (IPA). The IPA was replaced every 2 hours for 10hours. At the end of about 10 hours, 50% of the IPA was removed andreplaced with DI water and the jar was rolled for 20 minutes. After 20minutes, 50% of the IPA was removed and replaced with DI water and thejar was rolled for another 20 minutes. The lenses were transferred topacking solution, rolled for 20 minutes and then tested.

TABLE 5 Step 1 Step 1 Step 2 Step 2 Advancing intensity time intensitytime Contact Ex. # (mW/cm²) (min:sec) (mW/cm²) (min:sec) Angle 27 1.16:55 5.5 1:28 51 ± 1 28 1.1 2:46 5.5 2:21 55 ± 2 29 1.1 11:03  5.5 0:3555 ± 1 30 1.7 6:30 5.5 0:35 50 ± 1 31 1.7 1:37 5.5 2:21 55 ± 1 32 1.74:04 5.5 1:28 54 ± 2 33 2.4 2:52 5.5 1:28 62 ± 6 34 2.4 4:36 5.5 0:35 76± 9 35 2.4 1:09 5.5 0:35 78 ± 6

The contact angles for Examples 27 through 232 are not significantlydifferent, indicating that step 1 cure intensities of less than aboutabout 2 mW/cm² provide improved wettability for this lens formulationregardless of the step 1 cure time. However, those of skill in the artwill appreciate that shorter step 1 cure times (such as those used inExamples 28 and 31) allow for shorter overall cure cycles. Moreover, itshould be noted that even though the contact angles for Examples 33through 35 are measurably higher than those of Examples 27-32, thelenses of Examples 33-35 may still provide desirable on eye wettability.

Examples 36-41

The reaction components of Example 1, were blended with either 25% or40% D3O as diluent in accordance with the procedure of Example 1. Theresultant reaction mixtures were charged into plastic contact lens molds(made from Topas® copolymers of ethylene and norbornene obtained fromTicona Polymers) and cured in a glove box under a nitrogen atmosphere,at about 2.5 mW/cm² intensity, about 30 minutes and the temperaturesshown in Table 6, below. The lenses were removed from the molds,hydrated and autoclaved as describe in Example 1. After hydration thehaze values of the lenses were determined. The results shown in Table 6show that the degree of haziness was reduced at the higher temperatures.The results also show that as the concentration of diluent decreases thehaze also decreases.

TABLE 6 Ex. # % D30 Temp. (° C.) % haze DCA (°) 36 25 25 30 (6) 99 37 2550-55 12 (2) 100 38 25 60-65   14 (0.2) 59 39 40 25  50 (10) 68 40 4050-55 40 (9) 72 41 40 60-65 32 (1) 66 *Haze (std. dev.)

The results in Table 6 show that haze may be reduced by about 20%(Example 41 v. Example 39) and up to as much as about 65% (Example 37 v.Example 36) by increasing the cure temperature. Decreasing diluentconcentration from 40 to 25% decrease haze by between about 40 and 75%.

Examples 42-47

Lenses were made from the formulations shown in Table 8 using theprocedure of Example 1, with a 30 minute cure time at 25° C. and anintensity of about 2.5 mW/cm². Percent haze was measured and is reportedin Table 7.

TABLE 7 Ex. # 42 43 44 45 46 47 SiGMA 28.0 28.0 28.0 28.0 28.0 28.0mPDMS 31.0 31.0 28.0 28.0 28.0 28.0 acPDMS 0.0 0.0 4.0 4.0 4.0 4.0 (n =10) DMA 23.5 23.5 23.5 23.5 24.0 24.0 HEMA 6.0 6.0 5.0 5.0 6.0 6.0TEGDMA 1.5 1.5 1.5 1.5 0.0 0.0 Norbloc 2.0 2.0 2.0 2.0 2.0 2.0 PVP (K-7.0 7.0 7.0 7.0 7.0 7.0 90) CGI 1850 1.0 1.0 1.0 1.0 1.0 1.0 D30 25.0 4025.0 40.0 25.0 40.0 Properties Haze 30 50 7.3 14 26 25 Modulus 74 56 148104 74 NT (psi) Elongation 326 395 188 251 312 NT (%) EWC (%) 38 41 3335 38 39

A comparision of the results for formulations having the same amount ofdiluent and either TEGDMA or acPDMS (Examples 42 and 46 and Examples 43and 47) shows that acPDMS is an effective crosslinker and provideslenses with properties which are comparable to those where TEGDMA isused as a crosslinker. Examples 44 and 45 contain both crosslinkers.Haze for these Examples decreased substantially compared to the lensesmade from either crosslinker alone. However, modulus and elongation werenegatively impacted (likely because the amount of crosslinker was toogreat).

Examples 48-52

Reaction mixtures were made using the formulations shown in Table 8 witha mixture of 72.5% t-amyl alcohol and 27.5% PVP (M_(w)=2500) as thediluent. The reaction mixtures were placed into thermoplastic contactlens molds, and irradiated using Philips TL 20W/03T fluorescent bulbs at45° C., 0.8 mW/cm² for about 32 minutes. The molds were opened andlenses were released into deionized water at 95° C. over a period of 20minutes. The lenses were then placed into borate buffered salinesolution for 60 minutes and autoclaved at 122° C. and 30 minutes. Theproperties of the resulting lenses are shown in Table 9.

TABLE 8 Ex. # Components 48 49 50 51 52 53 54 SiGMA 30 30 30 33 34 25 20PVP 6 6 6 6 7 6 6 DMA 31 31 31 30 30 31 31 MPDMS 19 22 23.5 16.5 19 2528 AcPDMS 2 0 0 3 0 0 0 (n = 10) HEMA 9.85 8.5 6.95 9 6 10.5 12.5Norbloc 1.5 1.5 1.5 2 1.5 1.5 1.5 CGI 819 0.23 0.23 0.25 0.48 0 0.230.23 CGI 1850 0 0 0 0 1 0 0 EGDMA 0.4 0.75 0.8 0 0 0.75 0.75 TEGDMA 0 00 0 1.5 0 0 Blue HEMA 0.02 0.02 0 0 0 0.02 0.02 % Diluent* 40.0 40.027.3 39.4 25.9 40 40 Diluent comp A A B C D A A Properties EWC (%) 45 4547 49 47 49 50 DCA 52 (2) 51 (7) 74 (10) 108 75 (6) 47 (2) 56 (11)(advancing) Modulus (psi) 91 77 69 55 49 63 67 Elongation NT 232 167 275254 110 124 (%) Dk (barrers) 54 60 78 44 87 59 60 Diluents (weightparts): A = 72.5% t-amyl alcohol and 27.5 PVP (M_(W) = 2500) B = t-amylalcohol C = 15/38/38% TMP/2M2P/PVP (M_(W) = 2500) D = 57/43 2M2P/TMPNT—not tested

Thus, Examples 48, 51 show that formulations comprising both hydrophilic(EGDMA or TEGDMA) and hydrophobic crosslinkers (acPDMS) provide siliconehydrogel compositions which display an excellent balance of propertiesincluding good water content, moderate Dk, wettabiltiy, modulus andelongation.

Example 55

The lenses of Example 48 were clinically evaluated. The lenses were wornby 18 patients in a daily wear mode (nightly removal) for a period ofone week. At one week the PLTF-NIBUT was 8.4 (±2.9) seconds compared to7.0 (±1.3) seconds for ACUVUE® 2 lenses. The front surface discretedeposition was graded none to slight for 97% of the patients with thetest lenses, compared with 89% in control lenses. The movement wasacceptable for both test and control lenses.

Example 56

The lenses of Example 49 were clinically evaluated. The lenses were wornby 18 patients in a daily wear mode (nightly removal) for a period ofone week. At one week the PLTF-NIBUT was 8.4 (±2.9) seconds compared to7 (±1.3) seconds for ACUVUE® 2 lenses. The front surface discretedeposition was graded none to slight for 95% of the patients with thetest lenses, compared with 89% in control lenses. The movement wasacceptable for both test and control lenses.

Example 57

The lenses of Example 51 were clinically evaluated. The lenses were wornby 13 patients in a daily wear mode (nightly removal) for a period ofone week. At one week the PLTF-NIBUT was 4.3 (±1.9) seconds compared to9.6 (±2.1) seconds for ACUVUE® 2 lenses. The front surface discretedeposition was graded none to slight for 70% of the patients with thetest lenses, compared with 92% in control lenses. The movement wasacceptable for both test and control lenses. Thus, there is somecorrelation between contact angle measurements (108° for Example 51versus 52° for Example 48) and clinical wettability as measure byPLTF-NIBUT (4.3 seconds for Example 51 versus 8.4 seconds for Example48).

Examples 58-68

Silicone hydrogel lenses were made using the components listed in Table9 and the following procedure:

The components were mixed together in a jar to for a reaction mixture.The jar containing the reaction mixture was placed on a jar mill rollerand rolled overnight.

The reaction mixture was placed in a vacuum desiccator and the oxygenremoved by applying vacuum for 40 minutes. The desiccator was backfilled with nitrogen. Contact lenses were formed by adding approximately0.10 g of the degassed lens material to the concave front curve side ofTOPAS® mold cavities in a glove box with nitrogen purge. The molds wereclosed with polypropylene convex base curve mold halves. Polymerizationwas carried out under a nitrogen purge and was photoinitiated with 5 mWcm² of visible light generated using 20W fluorescent lights with a TL-03phosphor. After curing for 25 minutes at 45° C., the molds were opened.The concave front curve portion of the lens mold was placed into asonication bath (Aquasonic model 75D) containing deionized water underthe conditions (temperature and amount of Tween) shown in Table 10. Thelens deblock time is shown in Table 10. The lenses were clear and of theproper shape to be contact lenses.

TABLE 9 Ex. 58 Ex. 59 Ex. 60 Ex. 61 SiGMA 3.05 3.2 3.2 3.0 MPDMS 1.7 1.71.7 1.7 DMA 3.2 3.0 3.1 3.2 PVP 0.6 0.6 0.6 0.6 HEMA 1.0 0.8 0.8 1.0TEGDMA 0.2 0.4 0.3 0.2 Norblock 0.15 0.2 0.2 0.2 1850 0.1 0.1 0.3 0.3Triglide 1.5 1.5 1.5 2M2P 2.5 2.5 2.5 2.5 PVP low 0.5 1.5 1.5 0.5

TABLE 10 Form. Deblock time Ex. # Ex. # [Tween] (ppm) Temp (° C.) (min.)62 58 850 75 10 63 58 10,000 70 10-15 64 58 0 75 20-22 65 58 850 2210-15 66 59 850 85 3 67 60 850 85 6 68 61 850 75 18

Example 69

The lenses of Example 59 which were deblocked in Example 66, werefurther hydrated in deionized water at 65° C. for 20 minutes. The lenseswere then transferred into borate buffered saline solution and allowedto equilibrate for at least about 24 hours. The lenses were clear and ofthe proper shape to be contact lenses. The lenses had a water content of43%, a modulus of 87 psi, an elongation of 175%, and a Dk of 61barriers. The lenses were found to have an advancing contact angle of 57degrees. This indicates the lenses were substantially free ofhydrophobic material.

Example 70

The concave front curve portion of the lens mold from Example 61 wasplaced into a sonication bath (Aquasonic model 75D) containing about 5%DOE-120 in deionized water at about 75° C. The lenses deblocked from theframe in 18 minutes.

Example 71 Use of an Organic Solvent

The concave front curve portion of the lens mold from example 61 wasplaced into a sonication bath (Aquasonic 75D) containing about 10% of2-propanol an organic solvent in deionized water at 75° C. The lensesdeblocked form the frame in 15 minutes. When Tween was used as theadditive (Example 68) the deblock time was 18 minutes. Thus, the presentexample shows that organic solvents may also be used to deblock lensescomprising low molecular weight hydrophilic polymers.

Example 72 Contains No Low Molecular Weight PVP

Silicone hydrogel lenses wee made using the formulation and procedure ofExample 58, but without any low molecular weight PVP. The followingprocedure was used to deblock the lenses.

The concave front curve portion of the lens mold was placed into asonication bath (Aquasonic model 75D) containing about 850 ppm of Tweenin deionized water at about 65° C. The lenses did not release from themold. The deblock time for the formulation which contained low molecularweight hydrophilic polymer (Example 58 formuation) under similar deblockconditions (Example 62-850 ppm Tween and 75° C.) was 10 minutes. Thus,the present Example shows that deblocking cannot be accomplished inwater only, in this formulation without including low molecular weighthydrophilic polymer in the formulation.

Example 73

The concave front curve portion of the lens mold from example 72 wasplaced into a sonication bath (Aquasonic 75D) containing about 10% of2-propanol an organic solvent in deionized water at 75° C. The lensesdeblocked form the frame in 20 to 25 minutes. Thus, lenses of thepresent invention which do not contain low molecular weight hydrophilicpolymer may be deblocked using an aqueous solution comprising an organicsolvent.

Examples 74-76

Formulations were made according to Example 49, but with varying amountsof photoinitiator (0.23, 0.38 or 0.5 wt. %), curing at 45° C. withPhilips TL 20W/03T fluorescent bulbs (which closely match the spectraloutput of the visible light used to measure gel time) irradiating themolds at 2.0 mW/cm².

The advancing contact angles of the resulting lenses are shown in Table11.

TABLE 11 Ex. # Wt % Advancing DCA Gel time (sec) 74 0.23 59 (4) 65 750.38 62 (6) 57 76 0.5 80 (7) 51

Examples 77-79

Gel times were measured for the formulation of Example 1 at 45° C. at1.0, 2.5 and 5.0 mW/cm². The results are shown in Table 12.

TABLE 12 Intensity Ex. # (mW/cm²⁾ gel time (sec) 77 1 52 78 2.5 38 79 534

The results of Examples 74 through 76 and 77 through 79 compared withExamples 27-35, show that as gel times increase, wettability improves.Thus, gel points can be used, in coordination with contact anglemeasurements, to determine suitable cure conditions for a given polymerformulation and photoinitiator system.

Example 80 Macromer Preparation

To a dry container, which was housed in a dry box under nitrogen atambient temperature was added 30.0 g (0.277 mol) ofbis(dimethylamino)methylsilane (a water scavenger), a solution of 13.75ml of a 1M solution of TBACB (386.0 g TBACB in 1000 ml dry THF), 61.39 g(0.578 mol) of p-xylene, 154.28 g (1.541 mol) methyl methacrylate (1.4equivalents relative to initiator), 1892.13 (9.352 mol)2-(trimethylsiloxy)ethyl methacrylate (8.5 equivalents relative toinitiator) and 4399.78 g (61.01 mol) of THF. This mixture was charged toa dry, three-necked, round-bottomed flask equipped with a thermocoupleand condenser, all connected to a nitrogen source.

The initial mixture was cooled to 15° C. while stirring and purging withnitrogen. After the solution reached 15° C., 191.75 g (1.100 mol) of1-trimethylsiloxy-1-methoxy-2-methylpropene (1 equivalent) was injectedinto the reaction vessel. The reaction was allowed to exotherm toapproximately 62° C. and then 30 ml of a 0.40 M solution of 154.4 gTBACB in 11 ml of dry THF was metered in throughout the remainder of thereaction. After the temperature of reaction reached 30° C. and themetering began, a solution of 467.56 g (2.311 mol)2-(trimethylsiloxy)ethyl methacrylate (2.1 equivalents relative to theinitiator), 3636.6. g (3.463 mol) n-butylmonomethacryloxypropyl-polydimethylsiloxane (3.2 equivalents relative tothe initiator), 3673.84 g (8.689 mol) TRIS (7.9 equivalents relative tothe initiator) and 20.0 g bis(dimethylamino)methylsilane was added.

This mixture was allowed to exotherm to approximately 38-42° C. and thenallowed to cool to 30° C. At that time, a solution of 10.0 g (0.076 mol)bis(dimethylamino)methylsilane, 154.26 g (1.541 mol) methyl methacrylate(1.4 equivalents relative to the initiator) and 1892.13 g (9.352 mol)2-trimethylsiloxy)ethyl methacrylate (8.5 equivalents relative to theinitiator) was added and the mixture again allowed to exotherm toapproximately 40° C. The reaction temperature dropped to approximately30° C. and 2 gallons of THF were added to decrease the viscosity. Asolution of 439.69 g water, 740.6 g methanol and 8.8 g (0.068 mol)dichloroacetic acid was added and the mixture refluxed for 4.5 hours toremove the trimethylsiloxy protecting groups on the HEMA. Volatiles werethen removed and toluene added to aid in removal of the water until avapor temperature of 110° C. was reached. The reaction flask wasmaintained at approximately 110° C. and a solution of 443 g (2.201 mol)TMI and 5.7 g (0.010 mol) dibutyltin dilaurate were added. The mixturewas reacted until the isocyanate peak was gone by IR. The toluene wasevaporated under reduced pressure to yield an off-white, anhydrous, waxyreactive macromer. The macromer was placed into acetone at a weightbasis of approximately 2:1 acetone to macromer. After 24 hrs, water wasadded to precipitate out the macromer and the macromer was filtered anddried using a vacuum oven between 45 and 60° C. for 20-30 hrs.

Examples 81-88

Reaction mixtures were made in a nitrogen-filled glove box using theformulations shown in Table 12 with a D3O and/or IPL as the diluent. Thereaction mixtures were placed into thermoplastic contact lens molds, andirradiated using Philips TL 20W/03T fluorescent bulbs at 50° C., forabout 60 minutes. The molds were opened and lenses were released IPA,leached and transferred into borate buffered saline. The properties ofthe resulting lenses are shown in Table 13.

TABLE 13 Example Component 81 82 83 84 85 86 87 88 Macromer 18 18 13 1313 13 13 11 MPDMS 23 18 29 28 28 28 26 28 AcPDMS 5 10 3 3 3 5 5 5 (n =10) TRIS 14 14 15 15 15 14 13 14 DMA 27 27 28 29 30 30 33 32 HEMA 5 5 22 2 2 2 2 Norbloc 2 2 2 2 2 2 2 2 PVP K-90 5 5 7 6 5 5 5 5 Blue HEMA0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 CGI 1850 1 1 1 1 1 1 1 1 %Diluent 20 20 30 30 30 30 30 30 % D3O in dil. 60 60 100 100 100 60 100100 % IPL in dil. 40 40 0 0 0 40 0 0 EWC (%) 36 32 40 40 39 37 40 38 DCA48 46 45 50 57 (advancing) Modulus (psi) 149 268 85 90 91 107 134 129Elongation 216 149 294 300 290 251 176 209 (%) Dk (barrers) 89 76 114100 116 117

Example 89

The lenses of Example 83 were clinically evaluated. The lenses were wornby 10 patients in a daily wear mode (nightly removal) for a period of 30minutes. For each patient, the test lens was worn in one eye and anBauch & Lomb Purevision lens was worn in the contralateral eye. Atthirty minutes the PLTF-NIBUT was 7.5 (±1.6) seconds compared to 8.6(+1.6) seconds for the Bausch & Lomb Purevision lens. The front surfacediscrete deposition was graded none to slight for 100% of the patientswith the test lenses, compared with 100% in control lenses. The movementwas acceptable for both test and control lenses. The lenses of thepresent invention are comparable in performance to the B&L lens, whichhas a plasma coating. Thus, the present Example shows that lenses formedfrom a polymer network comprising a siloxane containing macromer, highmolecular weight hydrophilic polymer and a compatibilizing componentdisplay good wettability and deposition resistance without a coating.

Example 90

Trifluoromethane sulfonic acid (2.3 ml) was added to 27.8 g1,3-bis(hydroxybutyl)tetramethyldisiloxane and 204.4 goctamethylcyclotetrasiloxane. The resulting solution was stirredovernight. 17.0 g Na₂CO₃ were added and the mixture was stirred for onehour. About 50 ml hexane was added and the mixture was stirred for aboutone hour, then filtered. The hexane was evaporated under reducedpressure and cyclics were removed by heating to 110° C. at <1 mBar forabout one hour to produce hydroxybutyl terminated polydimethylsiloxane.

In a separate flask 12.2 g CH₂OH terminated Fluorolink® Polymer

Modifier D10 with an average equivalent weight of 500 (Ausimont USA,equivalent to Fomblin® ZDOL) was combined with 11.8 mg dibutyltindilaurate. The resulting solution was evacuated to about 20 mBar twice,each time refilling with dry N₂. 5.0 ml isophorone diisocyanate wasadded and the mixture was stirred overnight under N₂ to produce a clearviscous product.

47.7 g of the hydroxybutyl terminated polydimethylsiloxane from abovewas combined with 41.3 grams anhydrous toluene. This solution wascombined with the Fluorolink®-Isophorone diisocyanate product and theresulting mixture was stirred under nitrogen overnight. The toluene wasevaporated from the product over about 5 hours at <1 mBar. 3.6 g2-isocyanatoethyl methacrylate was added and the resulting mixture wasstirred under N₂ for four days to produce a slightly opaque viscousliquid fluorosilicone macromer.

Example 91

2.60 g of the fluorosilicone macromer made in Example 90 was combinedwith 1.12 g ethanol, 1.04 g TRIS, 1.56 g DMA, 32 mg Darocur 1173 toproduce a slightly hazy blend containing 18% diluent (ethanol). Contactlenses were made from this blend in plastic molds (Topas) curing 30minutes under fluorescent UV lamps at room temperature in a N₂atmosphere. The molds were opened, and the lenses released (deblocked)into ethanol. The lenses were leached with CH₂Cl₂ and then IPA for about30 minutes each at room temperature, then placed into borate bufferedsaline for about 2 hours and then autoclave at 121° C. for 30 minutes.The resulting lenses were tacky to the touch and had a tendency to stickto each other. The advancing DCA of these lenses was measured and isshown in Table 14.

Example 92-88

Reaction mixtures were made using the reactive components (amounts basedupon reactive components) shown in Table 14 and D30 as a diluent. Theamount of D3O is based upon the total amount of reactive components anddiluent. The reaction mixture and lenses were made using procedure ofExample 91. The resulting lenses were slippery to the touch and did notstick to each other.

The advancing DCA of these lenses was measured and is shown in

Table 14, below.

TABLE 14 Example Component (wt %) 92 93 94 Fluorosilicone macromer 49.728.5 19 TRIS 19.9 0 0 DMA 29.8 24.8 24.7 PVP (K90) 0 5 4.9 SiGMA 0 40.750.1 EGDMA 0 0.4 0.6 Darocur 1173 0.6 0.6 0.6 Diluent Ethanol D3O D3O %Diluent in final blend 18 18 18 Advancing DCA 132 (8) 69 (7) 59 (9)

Examples 92 through 94 clearly show that hydrophilic polymer may be usedto improve wettability. In these Examples contact angles are reduced byup to about 50% (Example 93) and up to about 60% (Example 94).Compositons comprising higher amounts of fluorosilicone macromer andhydrophilic polymer can also be made by functionalizing thefluorosilicone macromer to include active hydrogens.

Examples 95-95

Reaction mixtures were made using reactive components shown in

Table 15 and 29% (based upon all reactive components and diluent) t-amylalcohol as a diluent and 11% PVP 2,500 (based upon reactive components).Amounts indicated are based upon 100% reactive components. The reactionmixtures were placed into thermoplastic contact lens molds, andirradiated using Philips TL 20W/03T fluorescent bulb at 60° C., 0.8mW/cm² for about 30 minutes under nitrogen. The molds were opened andlenses were released into deionized water at 95° C. over a period of 15minutes. The lenses were then placed into borate buffered salinesolution for 60 minutes and autoclaved at 122° C. for 30 min. Theproperties of the resulting lenses are shown in Table 15.

TABLE 15 Ex. # Components 95 96 97 98 99 SiGMA 30 30 30 30 30 PVP 0 1 36 8 DMA 37 36 34 31 29 MPDMS 22 22 22 22 22 HEMA 8.5 8.5 8.5 8.5 8.5Norbloc 1.5 1.5 1.5 1.5 1.5 CGI 819 0.25 0.25 0.25 0.25 0.25 EGDMA 0.750.75 0.75 0.75 0.75 Properties DCA 122 (8)  112 (6)   66 (13) 58 (8) 54(3) (advancing) Haze 18 (4) 11 (1) 13 (1) 14 (2) 12 (1)

Table 15 shows that the addition of PVP dramatically decreases contactangle. As little as 1% decreases the dynamic contact angle by about 10%and as little as 3% decreases dynamic contact angle by about 50%. Theseimprovements are consistent with those observed for macromer basedpolymers, such as those in Examples 92-94.

Example 100

Preparation of mPDMS-OH (used in Examples 3)

96 g of Gelest MCR-E11 (mono-(2,3-epoxypropyl)-propyl ether terminatedpolydimethylsiloxane(1000 MW)), 11.6 g methacrylic acid, 0.10 gtriethylamine and 0.02 g hydroquinone monomethylether were combined andheated to 140° C. with an air bubbler and with stirring for 2.5 hours.The product was extracted with saturated aqueous NaHCO₃ and CH₂Cl₂. TheCH₂Cl₂ layer was dried over Na_(e) SO₄ and evaporated to give 94 g ofproduct. HPLC/MS was consistent with desired structure:

1. A wettable silicone hydrogel comprising the reaction product of atleast one siloxane containing macromer; at least one high molecularweight hydrophilic polymer; and at least one compatibilizing component.2. The hydrogel of claim 1 wherein said siloxane containing macromer ispresent in an amount between about 5% to about 50%.
 3. The hydrogel ofclaim 1 wherein the siloxane containing macromer or prepolymer ispresent in an amount between about 10% to about 50%.
 4. The hydrogel ofclaim 1 wherein the siloxane containing macromer or prepolymer ispresent in an amount between about 15% to about 45%.
 5. The hydrogel ofclaim 1 wherein said at least on siloxane containing macromer comprisesat least one siloxane group, and at least one second group selected fromthe group consisting of urethane groups, alkylene groups, alkylene oxidegroups, polyoxyalkalene groups, arylene groups, alkyl esters, amidegroups, carbamate groups, perfluoroalkoxy groups, isocyanate groups,combinations thereof.
 6. The hydrogel of claim 5 wherein said at leastone siloxane containing macromers is formed via polymerizing saidsiloxane group with at least one acrylic or methacrylic compound.
 7. Thehydrogel of claim 5 wherein said at least one siloxane containingmacromer is selected from the group consisting of methacrylatefunctionalized, silicone-fluoroether urethane macromers, methacrylatefunctionalized, silicone urethane macromers, styrene functionalizedprepolymers of hydroxyl functional methacrylates and siliconemethacrylates and vinyl carbamate functionalized polydimethylsiloxane 8.The hydrogel of claim 1 comprising about 1% to about 15% high molecularweight hydrophilic polymer.
 9. The hydrogel of claim 1 comprising about3% to about 15% high molecular weight hydrophilic polymer.
 10. Thehydrogel of claim 1 comprising about 5% to about 12% high molecularweight hydrophilic polymer.
 11. The silicone hydrogel of claim 14wherein said hydrophilic polymer is selected from the group consistingof polyamides, polylactones, polyimides, polylactams, functionalizedpolyamides, functionalized polylactones, functionalized polyimides,functionalized polylactams, and mixtures thereof.
 12. The siliconehydrogel of claim 14 wherein said hydrophilic polymer is selected fromthe group consisting of poly-N-vinyl pyrrolidone,poly-N-vinyl-2-piperidone, poly-N-vinyl-2-caprolactam,poly-N-vinyl-3-methyl-2- caprolactam,poly-N-vinyl-3-methyl-2-piperidone, poly-N-vinyl-4-methyl-2- piperidone,poly-N-vinyl-4-methyl-2-caprolactam, poly-N-vinyl-3-ethyl-2-pyrrolidone, and poly-N-vinyl-4,5-dimethyl-2-pyrrolidone,polyvinylimidazole, poly-N-N-dimethylacrylamide, polyvinyl alcohol,polyacrylic acid, polyethylene oxide, poly 2 ethyl oxazoline, heparinpolysaccharides, polysaccharides, mixtures and copolymers thereof 13.The hydrogel of claim 1, wherein the high molecular weight hydrophilicpolymer is poly-N-vinylpyrrolidone.
 14. The silicone hydrogel of claim 1wherein said compatibilzing component is a compound of Formula I or II

wherein: n is an integer between 3 and 35 R¹ is hydrogen, C₁₋₆alkyl,R²,R³, and R⁴, are independently, C₁₋₆alkyl, triC₁₋₆alkylsiloxy, phenyl,naphthyl, substituted C₁₋₆alkyl, substituted phenyl, or substitutednaphthyl where the alkyl substitutents are selected from one or moremembers of the group consisting of C₁₋₆alkoxycarbonyl, C₁₋₆alkyl,C₁₋₆alkoxy, amide, halogen, hydroxyl, carboxyl, C₁₋₆alkylcarbonyl andformyl, and where the aromatic substitutents are selected from one ormore members of the group consisting of C₁₋₆alkoxycarbonyl, C₁₋₆alkyl,C₁₋₆alkoxy, amide, halogen, hydroxyl, carboxyl, C₁₋₆alkylcarbonyl andformyl; R⁵ is a hydroxyl, an alkyl group containing one or more hydroxylgroups, or (CH₂(CR⁹R¹⁰)_(y)O)_(x))—R¹¹ wherein y is 1 to 5, preferably 1to 3, x is an integer of 1 to 100, preferably 2 to 90 and morepreferably 10 to 25; R⁹-R¹¹ are independently selected from H, alkylhaving up to 10 carbon atoms and alkyls having up to 10 carbon atomssubstituted with at least one polar functional group; R⁶ is a divalentgroup comprising up to 20 carbon atoms; R⁷ is a monovalent group thatcan undergo free radicals or cationic polymerization, comprising up to20 carbon atoms, and R8 is is a divalent or trivalent group comprisingup to 20 carbon atoms.
 15. The silicone hydrogel of claim 1 wherein saidhydroxyl-functionalized silicone-containing monomer is selected from thegroup consisting of 2-propenoic acid,2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[trimethylsilyl)oxy]disiloxanyl]propoxy]propylester,(3-methacryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane,(2-methacryloxy-3-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilaneand mixtures thereof.
 16. The hydrogel of claim 1 wherein saidcompatibilizing component comprises at least one compound of FormulaIII:IWA-HB-[IWA-HB]_(x)-IWA Wherein x is 1 to 10; IWA is a difunctionalhydrophilic polymer having a number average molecular weight of betweenabout 1000 and about 50,000 Daltons; and HB is a difunctional moeitycomprising at least one N which is capable of hydrogen bonding.
 17. Thehydrogel of claim 16 wherein said IWA is derived from {acute over(α)},ω-hydroxyl terminated PVP and {acute over (α)},ω-hydroxylterminated polyoxyalkylene glycols.
 18. The hydrogel of claim 16 whereinHB is a difunctional group selected from the group consisting of amides,imides, carbamates ureas, and combinations thereof.
 19. The hydrogel ofclaim 1 wherein said compatibilizing component is present in an amountbetween about 5 and about 90 weight %.
 20. The hydrogel of claim 1further comprising at least one oxygen permeable component in additionto said siloxane containing macromer or prepolymer.
 21. The hydrogel ofclaim 20 wherein said oxygen permeable component is selected from thegroup consisting of amide analogs of3-methacryloxypropyltris(trimethylsiloxy)silane; siloxane vinylcarbamate analogs, siloxane vinyl carbonate analogs, and siloxanecontaining monomers, combinations and oligomers thereof.
 22. Thehydrogel claim 20 wherein said oxygen permeable component is selectedfrom the group consisting of3-methacryloxypropyltris(trimethylsiloxy)silane, monomethacryloxypropylterminated polydimethylsiloxanes, polydimethylsiloxanes,3-methacryloxypropylbis(trimethylsiloxy)methylsilane,methacryloxypropylpentamethyl disiloxane and combinations thereof. 23.The hydrogel of claim.20 wherein said oxygen permeable component ispresent in an amount of 0 to about 80 weight %.
 24. The hydrogel of 20wherein said oxygen permeable component is present in an amount of about5 to about 60%.
 25. The hydrogel of claim 20 wherein said oxygenpermeable component is present in an amount of about 10 to about 40%.26. The hydrogel of claim 1 further comprising at least one hydrophilicmonomer.
 27. The hydrogel claim 26 wherein said at least one hydrophilicmonomer comprises at least one acrylic group, vinyl group or acombination thereof.
 28. The hydrogel of claim 27 wherein said acrylicgroup has the formula CH₂═CRCOX, where R is hydrogen or C₁₋₆alkyl and Xis O or N.
 29. The hydrogel of claim 26 wherein said at least onehydrophilic monomer is selected from the group consisting ofN,N-dimethylacrylamide, 2-hydroxyethyl methacrylate, glycerolmethacrylate, 2-hydroxyethyl methacrylamide, polyethyleneglycolmonomethacrylate, methacrylic acid, acrylic acid, N-vinyl pyrrolidone,N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethylformamide, N-vinyl formamide, hydrophilic vinyl carbonate monomers,vinyl carbamate monomers, hydrophilic oxazolone monomers, polydextranand copolymers and combinations thereof.
 30. The hydrogel of claim 26wherein said at least one hydrophilic monomer comprises at least onepolyoxyethylene polyols having one or more of the terminal hydroxylgroups replaced with a functional group containing a polymerizabledouble bond.
 31. The hydrogel of claim 26 wherein said at least onehydrophilic monomer is selected from the group consisting ofpolyethylene glycol, ethoxylated alkyl glucoside, and polyethylenepolyols having one or more terminal polymerizable olefinic groups bondedto the polyethylene polyol.
 32. The hydrogel of claim 26 wherein said atleast one hydrophilic monomer is selected from the group consisting ofN,N-dimethylacrylamide, 2-hydroxyethyl methacrylate, glycerolmethacrylate, 2-hydroxyethyl methacrylamide, N-vinylpyrrolidone,polyethyleneglycol monomethacrylate, methacrylic acid, acrylic acid andcombinations thereof.
 33. The hydrogel of claim 26 wherein said at leastone hydrophilic monomer comprises N,N-dimethylacrylamide.
 34. Thehydrogel of claim 26 wherein said at least one hydrophilic monomer ispresent in amounts of about 0 to about 70 weight %.
 35. The hydrogel ofclaim 26 wherein said at least one hydrophilic monomer is present inamounts of about 5 to about 60 weight %.
 36. The hydrogel of claim 26wherein said at least one hydrophilic monomer is present in amounts ofabout 10 to 50 weight %.
 37. The hydrogel of claim 1 comprising about 1to about 15 weight % high molecular weight hydrophilic polymer and about5 to about 90 weight % hydroxyl-functionalized silicone-containingmonomer.
 38. The hydrogel of claims 1 comprising about 1% to about 15%high molecular weight hydrophilic polymer; about 5 to about 90 weight %compatibilizing component; about 5 to about 50 weight % said siloxanecontaining macromer, 0 to about 80 weight % siloxane containing monomerand 0 to about 70 weight % hydrophilic monomer.
 39. The hydrogel ofclaim 1 comprising about 3% to about 15% high molecular weighthydrophilic polymer; about 10 to about 80 weight % compatibilizingcomponent; about 10 to about 50 weight % said siloxane containingmacromer or prepolymer, 5 to about 60 weight % siloxane containingmomoner and 5 to about 60 weight % hydrophilic monomer.
 40. The hydrogelof claim 1 comprising about 5% to about 12% high molecular weighthydrophilic polymer; about 15 to about 55 weight % compatibilizingcomponent; about 15 to about 45 weight % said siloxane containingmacromer, 10 to about 40 weight % oxygen permeable component and 10 toabout 50 weight % hydrophilic monomer.
 41. A silicone hydrogel contactlens comprising the hydrogel of claim 1 and wherein said contact lens isnot surface modified.
 42. The lens of of claim 41, wherein the contactlens is a soft contact lens.
 43. The lens of claim 41 wherein said lenshas an advancing dynamic contact angle of less than about 70°.
 44. Thelens of claim 41 wherein said lens has an advancing dynamic contactangle of less than about 60°.
 45. The lens of claim 41 wherein saidlens, after about one day of wear, has a tear film break up time of atleast about 7 seconds.
 46. The lens of claim 41 wherein said lensfurther comprises a modulus of less than about 90 psi.
 47. The lens ofclaims 41 wherein said lens further comprises a water content betweenabout 10 and about 60%.
 48. The hydrogel of claim 1 wherein said highmolecular weight hydrophilic polymer is present in an amount sufficientto provide an article formed from said hydrogel with an advancingdynamic contact angle which is at least about 10% lower than a hydrogelwithout said hydrophilic polymer.
 49. The hydrogel of claim 1 whereinsaid hydrogel is an interpenetrating network or a semi-interpenetratingnetwork.
 50. A method comprising the steps of (a) mixing at least onediluent which is water soluble at processing conditions and reactivecomponents comprising at least one high molecular weight hydrophilicpolymer, at least one siloxane containing macromer and an effectiveamount of at least one compatibilizing component to form a reactionmixture and (b) curing the product of step (a) to form a biomedicaldevice; (c) removing said biomedical device from a mold in which saidbiomedical device was cured and (d) hydrating said biomedical device,wherein both steps (c) and (d) are performed in aqueous solutions whichcomprise water as a substantial component.
 51. The method of claim 50wherein said biomedical device comprises an ophthalmic device.
 52. Themethod of claim 50 wherein said ophthalmic device is a silicone hydrogelcontact lens.
 53. (canceled)
 54. The method of claim 50 wherein saiddiluent is selected from the group consisting of ethers, esters,alkanes, alkyl halides, silanes, amides, alcohols and mixtures thereof.55. The method of claim 50 wherein said diluent selected from the groupconsisting amides, alcohols and mixtures thereof.
 56. The method ofclaim 50 wherein said diluent selecting the group consisting oftetrahydrofuran, ethyl acetate, methyl lactate, i-propyl lactate,ethylene chloride, octamethylcyclotetrasiloxane, dimethyl formamide,dimethyl acetamide, dimethyl propionamide, N methyl pyrrolidinonemixtures thereof and mixtures of any of the foregoing with at least onealcohol.
 57. The method of claim 50 wherein said diluent comprises atleast one alcohol having at least 4 carbon atoms.
 58. The method ofclaim 50 wherein said diluent comprises at least one alcohol having atleast 5 carbons atoms.
 59. The method of claim 50 wherein said diluentsare inert and easily displaceable with water.
 60. The method of claim 50wherein said diluent comprises at least one alcohol selected from thegroup consisting of tert-butanol, tert-amyl alcohol, 2-butanol,2-methyl-2-pentanol, 2,3-dimethyl-2-butanol, 3-methyl-3-pentanol,3-ethyl-3-pentanol, 3,7-dimethyl-3-octanol and mixtures thereof.
 61. Themethod of claim 50 wherein said diluent is selected from the groupconsisting of hexanol, heptanol, octanol, nonanol, decanol, tert-butylalcohol, 3-methyl-3-pentanol, isopropanol, t amyl alcohol, ethyllactate, methyl lactate, i-propyl lactate, 3,7-dimethyl-3-octanol,dimethyl formamide, dimethyl acetamide, dimethyl propionamide, N methylpyrrolidinone and mixtures thereof.
 62. The method of claim 50 whereinsaid diluent is selected from the group consisting of1-ethoxy-2-propanol, 1-methyl-2-propanol, t-amyl alcohol, tripropyleneglycol methyl ether, isopropanol, 1-methyl-2-pyrrolidone,N,N-dimethylpropionamide, ethyl lactate, dipropylene glycol methyl etherand mixtures thereof.
 63. The method of claim 50 wherein said diluent ispresent in an amount less than about 40 weight % based upon the reactionmixture.
 64. The method of claim 50 wherein said diluent is present inan amount between about 10 and about 30 weight % based upon the reactionmixture.
 65. (canceled)
 66. The method of claim 5350 wherein said curingis conducted via heat, exposure to radiation or a combination thereofand said reaction mixture further comprises at least one initiator. 67.The method of claim 66 wherein said curing is conducted via irradiationcomprises ionizing and/or actinic radiation and said initiator comprisesat least one photoinitiator.
 68. The method of claim 67 wherein saidradiation comprises light having a wavelength of about 150 to about 800nm and said initiator is selected from the group consisting of aromaticalpha-hydroxy ketones, alkoxydoxybenzoins, acetophenones, acyl phosphineoxides, mixtures of tertiary amines and diketones, and mixtures thereof.69. The method of claim 67 wherein said initiator is selected from thegroup consisting of 1-hydroxycyclohexyl phenyl ketone,2-hydroxy-2-methyl-1-phenyl-propan-1-one,bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentyl phosphine oxide,bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide,2,4,6-trimethylbenzyldiphenyl phosphine oxide and2,4,6-trimethylbenzyoyl diphenylphosphine oxide, benzoin methyl ester,combinations of camphorquinone and ethyl 4-(N,N-dimethylamino)benzoateand mixtures thereof.
 70. The method of claim 67 wherein said initiatoris present in the reaction mixture in amounts from about 0.1 to about 2weight percent based upon said reactive components.
 71. The method ofclaim 67 wherein said curing is conducted via visible light irradiation.72. The method of claim 71 wherein said initiator comprises1-hydroxycyclohexyl phenyl ketone,bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentyl phosphine oxide andmixtures thereof.
 73. The method of claim 71 wherein said initiatorcomprises bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide.
 74. Themethod of claims 67 wherein said reactive components further comprisesat least one UV absorbing compound.
 75. The method of claim 71 whereinsaid curing step is conducted at a cure intensity between about 0.1 andabout 6 mW/cm².
 76. The method of claim 71 wherein said curing step isconducted at a cure intensity of between about. 0.2 mW/cm² to about 3mW/cm².
 77. The method of claims 75 wherein said curing step furthercomprises a cure time of at least about 1 minute.
 78. The method ofclaims 75 wherein said curing step further comprises a cure time ofbetween about 1 and about 60 minutes.
 79. The method of claim 75 whereinsaid curing step further comprises a cure time of between about 1 andabout 30 minutes.
 80. The method of claim 75 wherein said curing step isconducted at a temperature greater than about 25° C.
 81. The method ofclaim 75 wherein said curing step is conducted at a temperature betweenabout 25° C. and 70° C.
 82. The method of claim 75 wherein said curingstep is conduct at a temperature between about 40° C. and 70° C.
 83. Themethod of claim 5350 wherein said reaction mixture is cured in a moldand said method further comprises the step deblocking said ophthalmicdevice from said mold.
 84. The method of claim 83 wherein said reactionmixture further comprises at least one low molecular weight hydrophilicpolymer.
 85. The method of claim 84 wherein said low molecular weighthydrophilic polymer has a number average molecular weight of less thanabout 40,000 Daltons.
 86. The method of claim 84 wherein said lowmolecular weight hydrophilic polymer has a number average molecularweight of less than about 20,000 Daltons.
 87. The method of claim 84wherein the low molecular weight polymer is selected from the groupconsisting of water soluble polyamides, lactams and polyethyleneglycols, and mixtures thereof.
 88. The method of claim 84 wherein thelow molecular weight polymer is selected from the group consistingpoly-vinylpyrrolidone, polyethylene glycols, poly 2 ethyl-2-oxazolineand mixtures thereof.
 89. The method of claim 84 wherein the lowmolecular weight hydrophilic polymer is present in amounts up to about20 weight % based upon the reaction mixture.
 90. The method of claim 84wherein the low molecular weight hydrophilic polymer is present inamounts between about 5 and about 20 weight % based upon the reactionmixture.
 91. The method of claim 84 wherein said deblocking is conductedusing an aqueous solution.
 92. The method of claim 84 wherein saidaqueous solution further comprises at least one surfactant.
 93. Themethod of claim 92 wherein said surfactant comprises at least onenon-ionic surfactant.
 94. The method of claim 92 wherein said surfactantcomprises TWEEN®, or DOE120.
 95. The method of claim 92 wherein saidsurfactant is present in amounts up to about 10,000 ppm.
 96. The methodof claim 92 wherein said surfactant is present in amounts between about100 and about 1200 ppm.
 97. The method of claim 83 wherein said aqueoussolution comprises at least one organic solvent.
 98. The method of claim83 wherein said deblocking is conducted at a temperature between aboutambient and about 100° C.
 99. The method of claim 83 wherein saiddeblocking is conducted at a temperature between about 70° C. and about95° C.
 100. The method of claim 83 wherein said deblocking is conductedusing agitation.
 101. The method of claim 83 wherein said agitationcomprises sonication.
 102. A method comprising the steps of (a) mixingreactive components comprising a high molecular weight hydrophilicpolymer and an effective amount of a compatibilizing component and (b)curing the product of step (a) at or above a minimum gel time, to form awettable biomedical device.
 103. The method of claim 102 wherein saiddevice is a ophthalmic lens.
 104. The method of claim 103 wherein saiddevice is a contact lens.
 105. The method of claim 103 wherein said lenscomprises an advancing dynamic contact angle of about 80° or less. 106.The method of claim 103 wherein said lens comprises an advancing dynamiccontact angle of about 70° or less.
 107. The method of claim 103 whereinsaid lens comprises a tear film break up time of at least about 7seconds.
 108. The method of claim 103 wherein said reactive componentsfurther comprises at least one initiator
 109. The method of claim 108wherein said cure is conducted via irradiation and said conditionscomprise an initiator concentration and cure intensity effective toprovide said minimum gel time.
 110. The method of claim 109 wherein saidinitiator is present in an amount up to about 1% based upon all reactivecomponents.
 111. The method of claim 109 wherein said initiator ispresent in an amount less than about 0.5% based upon all reactivecomponents.
 112. The method of claim 109 wherein said cure is conductedvia irradiation at an intensity of less than about 5 mW/cm².
 113. Themethod of claim 109 wherein said gel time is at least about 30 seconds.114. The method of claim 109 wherein said gel time is at least about 35seconds.
 115. The method of claim 102 wherein said compatibilizingcomponent is not a hydroxyl functionalized macromer made by grouptransfer polymerization.
 116. The method of claim 102 wherein saidreactive components further comprise at least one macromer.
 117. Themethod of claim 50 wherein said compatibilizing component is not ahydroxyl functionalized macromer made by group transfer polymerization.118. A method for improving the wettability of an ophthalmic deviceformed from a reaction mixture comprising adding at least one highmolecular hydrophilic weight polymer and a compatibilizing effectiveamount of at least one compatibilizing component to said reactionmixture, wherein said compatibilizing component is not a styrenefunctionalized prepolymer made from hydroxyl functional methacrylates.119. The method of claim 118 wherein said compatibilizing component hasa compatibility index of greater than about 0.5.
 120. The method ofclaim 118 wherein said compatibilizing component has a compatibilityindex of greater than about
 1. 121. The method of claim 118 wherein saidcompatibilizing component comprises at least one siloxane group. 122.The method of claim 121 wherein said compatibilizing component furthercomprises hydroxyl functionality and has a Si to OH ratio of less thanabout 15:1.
 123. The method of claim 121 wherein said compatibilizingcomponent has a Si to OH ratio of between about 1:1 to about 10:1. 124.An ophthalmic lens comprising a silicone hydrogel which has, withoutsurface treatment, a tear film break up time of at least about 7 seconds125. A silicone hydrogel contact lens comprising at least one oxygenpermeable component, at least one compatibilizing component and anamount of high molecular weight hydrophilic polymer sufficient toprovide said device, without a surface treatment, with tear film breakup time after about one day of wear of at least about 7 seconds.
 126. Adevice comprising a silicone hydrogel contact lens which issubstantially free from surface deposition without surface modification.